Block polyorganosiloxane block organomer polymers and release agents

ABSTRACT

A polyorganosiloxane block hydrocarbyl block polymer having utility as a release agent in toner fusing systems. The polymer has one or more polar linkages, with each such linkage bonding a polyorganosiloxane block and a hydrocarbyl block, and also including a polar functionality.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit under 35 USC §119(e) of prior U.S.Provisional Patent Application No. 60/386,040, filed Jun. 5, 2002. Thisprovisional patent application is incorporated herein in its entirety,by reference thereto.

Filed concurrently with this application is U.S. application Ser. No.10/454,900, filed Jun. 5, 2003, entitled “Molecular Complexes andRelease Agents”. This concurrently filed application is incorporatedherein in its entirety, by reference thereto.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a composition comprising a releaseagent, for application to one or more fuser members and the substrate intoner fusing systems and processes. The present invention furtherrelates to combating toner offset by means of applying the compositionas indicated to one or more fuser members in toner fusing systems andprocesses.

2. Description of Background and Other Information

Generally in electrostatographic reproduction, the original to be copiedis rendered in the form of a latent electrostatic image on aphotosensitive member. This latent image is made visible by theapplication of electrically charged toner.

The toner thusly forming the image is transferred to a substrate—alsoreferred to in the art as a receiver—such as paper or transparent film,and fixed or fused to the substrate. Where heat softenable toners—forexample, comprising thermoplastic polymeric binders—are employed, theusual method of fixing the toner to the substrate involves applying heatto the toner, once it is on the substrate surface, to soften it, andthen allowing or causing the toner to cool. This application of heat inthe fusing process is preferably at a temperature of about 90° C.-220°C.; pressure may be employed in conjunction with the heat.

A system or assembly for providing the requisite heat and pressure isgenerally provided as a fusing subsystem, and customarily includes afuser member and a support member. The various members that comprise thefusing subsystem are considered to be fusing members; of these, thefuser member is the particular member that contacts the toner to befused by the fusing subsystem. The heat energy employed in the fusingprocess generally is transmitted to toner on the substrate by the fusermember. Specifically, the fuser member is heated; to transfer heatenergy to toner situated on a surface of the substrate, the fuser membercontacts this toner, and correspondingly also can contact this surfaceof the substrate itself. The support member contacts an opposing surfaceof the substrate.

Accordingly, the substrate can be situated or positioned between thefuser and support members, so that these members can act together on thesubstrate to provide the requisite pressure in the fusing process. Incooperating, preferably the fuser and support members define a nip, orcontact arc, in which the substrate is positioned or resides, and/orthrough which the substrate passes. Also as a matter of preference, thefuser and support members are in the form of fuser and pressure rollers,respectively. Yet additionally as a matter of preference, one or both ofthe fuser and support members have a soft layer that increases the nip,to effect better transfer of heat to fuse the toner.

During the fusing process toner can be offset from the substrate to thefuser member. Toner thusly transferred to the fuser member in turn maybe passed on to other members in the electrostatographic apparatus, orto subsequent substrates subjected to fusing.

Toner on the fusing member therefore can interfere with the operation ofthe electrostatographic apparatus and with the quality of the ultimateproduct of the electrostatographic process. This offset toner isaccordingly regarded as contamination of the fuser member, andpreventing or at least minimizing this contamination is a desirableobjective.

Toner offset is a particular problem when polyester toners are used.Polyester toners are frequently used in high quality color and black andwhite printing applications. In particular, offset to the fuser membercan collect on other members of the fusing subsystem, such as externalheating members for heating fuser members, and release agentapplicators—e.g., oilers.

In this regard, release agents can be applied to fusing members duringthe fusing process, to combat toner offset. These agents usually are orinclude polyorganosiloxanes, particularly polyorganosiloxane oils. Thepolysiloxanes have antiadhesive properties that are favorable forprotecting the surface of the fuser member, and maintaining thedurability of the fuser member.

Modified polysiloxanes having functional groups provide a protectivebarrier by attaching to the fuser surface via specific interactionsbetween the functional groups and the fuser surface. The interaction ofthe functional groups with the fuser surface allows the polysiloxane tosterically block contact of the toner with the fuser member surface andprovide a protective barrier. Monofunctional polysiloxanes with onereactive functional group may interact with the fuser member or tonersurface to provide a protective coating as well as increase the wettingof nonfunctional components in the polymeric release agent composition.Multifunctional polysiloxanes with more than one reactive group alsointeract in the same manner to provide a protective coating; however,the presence of more than one functional group may allow undesiredadditional interaction with other components.

As to functional polyorganosiloxanes, U.S. Pat. No. 6,261,688 and U.S.Publication No. 2001/0019768 disclose polymeric release agentscomprising organosiloxane polymers with tertiary amino functionalgroups. Among the tertiary amino functional groups disclosed are thosewhere the N atom has an alkyl or arylalkyl as one substituent group, andan acyl [—C(═O)—CH₃] group as the other.

Further, U.S. Pat. No. 5,157,445 discloses a toner release oilcomposition containing an organopolysiloxane with one or more secondaryamino substituents, where the secondary amine N atom has a C₁₋₈ alkylenesubstituent terminated by NH₂. Also disclosed as eligible release oilingredients are organopolysiloxanes having aromatic secondary aminosubstituents.

U.S. Pat. Nos. 5,531,813 and 5,512,409 disclose secondary aminofunctional polyorganosiloxanes, where the N atom can have—besides the Hatom—a C₁₋₁₈ alkyl or arylalkyl substituent. These patents also disclosethe polyorganosiloxanes as monoamino functional polymers, with themonoamino functionality interacting with the hydrofluoroelastomersurface of a fuser member; this interaction is stated to provide abarrier to the toner, as well as a low surface energy film to releasethe toner from the surface. Additionally as to monoamino functionalityin particular, branched T-type monoamino functional polysiloxanes, inwhich the reactive group is attached to a central silicon atom, aredisclosed in U.S. Pat. No. 5,516,361.

Functional polysiloxanes also are described in U.S. Pat. No. 4,101,686,which discloses polymeric release agents having functional groups suchas carboxyl, hydroxy, epoxy, amino, isocyanate, thioether, and mercaptogroups. This patent states that the polymeric release agents are appliedto a heated fuser member to prevent toner adhesion. Similarly, U.S. Pat.Nos. 4,272,179 and 4,264,181 disclose polymeric release agents whichhave functional groups, and which are applied to the surface of a fusermember.

Additionally, U.S. Pat. Nos. 5,141,788 and 5,281,506 disclose a fusermember comprising a polyorganosiloxane having reactive functional groupswhich is grafted to the surface of the cured fluoroelastomer layer. U.S.Pat. No. 4,853,737 also discloses a fuser roller having an outer layercomprising a cured fluoroelastomer, with polydiorganosiloxane segmentsthat are covalently bonded to the backbone of the fluoroelastomer; thepolydiorganosiloxanes have functional groups, at least one of which ispresent on the polydiorganosiloxane chain to form the covalent bond tothe fluoroelastomer backbone.

U.S. Provisional Patent Application No. 60/305,874, filed Jul. 18, 2001,discloses monofunctional branched polysiloxanes, wherein the branchedsiloxane chain provides enhanced coverage of the surface and resistanceto extension under shear. This provisional application is incorporatedherein in its entirety, by reference thereto.

In addition to functional groups, polysiloxane release fluids have beenmodified with nonreactive organo groups that promote interaction orwetting of surface components. U.S. Pat. No. 5,780,545 discloses astabilized polyether modified organosiloxane that acts as a surfactantto promote wetting and that reduces offset. U.S. Pat. Nos. 5,568,239,5,641,603, 5,627,000, and 5,636,012 disclose polyorganosiloxanesmodified with side groups or end groups of fluorocarbon chains, forpromoting the wetting of fluorocarbon surfaces such astetrafluoroethylene. U.S. Pat. Nos. 5,783,719 and 5,959,056 discloselong chain hydrocarbon modification of organosiloxanes as solid releaseagents, and as being useful for other purposes—e.g., sealing tonercartridges; further, it is suggested that the long hydrocarbon chain mayalso act as a surfactant for the toner.

It would be desirable to have an agent that promotes wetting as asurfactant, and that also exhibits reactivity to and/or interaction withpolar sites—on the toner, or on the fuser member surface—to act againstor combat adherence of the toner to surfaces, or to polar sites on fusermembers, that tend to attract toner offset. It would further bedesirable that the composition could be easily prepared. It would yetadditionally be desirable that the composition have labile hydrogen forreacting to surfaces.

SUMMARY OF THE INVENTION

The present invention is characterized by novel block polyorganosiloxaneblock organomer polymers—the organomer or organomers being selected fromhydrocarbons and perhalopolyethers—that exhibit improved wetting oftoner surfaces, while still interacting with polar sites to combat—e.g.,prevent or prohibit, or at least inhibit, or lessen, or reduce—toneroffset. The present invention further provides novel blockpolyorganosiloxane block organomer polymers that demonstrate improvedwetting of fluorocarbon surfaces, while still interacting with polarsites to prevent toner offset.

The novel block polyorganosiloxane block organomer polymers of theinvention may be used for imparting—to the fusing member substratesurfaces, and to toner residing or contacting thereon—resistance totoner offset and accumulation on fusing members. In this regard, theinvention pertains to a composition for acting against, orcombating—e.g., preventing or prohibiting, or at least inhibiting, orlessening, or reducing—toner offset and buildup on fusing members.

The invention further pertains to a process for fusing toner residing ona substrate surface to the substrate surface. This process comprisesapplying, to the surface of a fuser member, novel blockpolyorganosiloxane block organomer polymer of the invention as apolymeric release agent, and contacting the toner with the fuser membersurface bearing this composition.

The invention further describes a method for preparing the release agentof the invention.

DESCRIPTION OF THE INVENTION

Copolymers are understood as including polymers incorporating twomonomeric units, i.e., bipolymers, as well as polymers incorporatingthree or more different monomeric units, e.g., terpolymers,tetrapolymers, quaterpolymers, etc.

Polyorganosiloxanes are understood as including functional andnonfunctional polyorganosiloxanes. Polyorganosiloxanes further areunderstood as including polydiorganosiloxanes—i.e., having two organogroups attached to each, or substantially each, or essentially each, ofthe polymer siloxy repeat units. Polyorganosiloxanes yet further areunderstood as including polydimethylsiloxanes.

Functional polyorganosiloxanes are understood as beingpolyorganosiloxanes having functional groups on the backbone, connectedto the polysiloxane portion, which can react with fillers present on thesurface of the fuser member, or with a polymeric fuser member surfacelayer or component thereof. Functional polyorganosiloxanes further areunderstood as being polyorganosiloxanes having functional groups such asamino, hydride, halo (including chloro, bromo, fluoro, and iodo),carboxy, hydroxy, epoxy, isocyanate, thioether, and mercapto functionalgroups. Nonfunctional polyorganosiloxanes further are understood asbeing polyorganosiloxanes without groups of the type as indicated.

The term “hydrocarbyl” is understood as including “aliphatic”,“cycloaliphatic”, and “aromatic”, and “hydrocarbyl” further isunderstood as including saturated, unsaturated, linear, branched,cyclic, and acyclic “hydrocarbyl”. “Hydrocarbyl” is also understood asincluding “alkyl”, “alkenyl”, “alkynl”, “cycloalkyl”, “aryl”, “aralkyl”,and “alkaryl”. Additionally, “hydrocarbyl” is understood as includingboth nonsubstituted hydrocarbyl and substituted hydrocarbyl, with theformer referring to the hydrocarbyl consisting of, or consistingessentially of, carbon and hydrogen atoms, and the latter referring tothe hydrocarbyl bearing one or more additional substituents. The one ormore additional substituents can be present along with carbon andhydrogen atoms, and or can be present in place of one, or more, or all,of the hydrogen atoms. Substituted hydrocarbyl encompasses halocarbyl(e.g., chloro, bromo, iodo, and especially fluorocarbyl), particularlyhaloalkyl (e.g., chloro, bromo, iodo, and especially fluoroalkyl), andencompasses fully and partially halogenated (e.g., chlorinated,brominated, iodinated, and especially fluorinated) hydrocarbyl,including perhalocarbyl (e.g., perchloro, perbromo, periodo, andperfluorocarbyl), and particularly perhaloalkyl (e.g., perchloro,perbromo, periodo, and especially perfluoroalkyl).

Further with respect to the foregoing, “hydrocarbyl” is understood asincluding nonhalogenated hydrocarbyl, which refers to hydrocarbyl thatis free, or at least essentially free, or at least substantially free,of halogenation—i.e., of chlorine, bromine, iodine, and fluorine atoms.Correspondingly, “hydrocarbyl” is understood as includingnonfluorinated, nonchlorinated, nonbrominated, and noniodinatedhydrocarbyl; these refer to hydrocarbyl that is free, or at leastessentially free, or at least substantially free, respectively,specifically of fluorination (i.e., of fluorine atoms), chlorination(i.e., of chlorine atoms), bromination (i.e., of bromine atoms), andiodination (i.e., of iodine atoms).

The term “organo” as used herein, such as in the context ofpolyorganosiloxanes, includes hydrocarbyl. Preferred organo groups forthe polyorganosiloxanes are the alkyl, aryl, and aralkyl groups.Particularly preferred alkyl, aryl, and aralkyl groups are the C₁-C₁₈alkyl, aryl, and aralkyl groups, particularly the methyl and phenylgroups.

It is understood that use conditions are those conditions, such astemperature, at which the release agent of the invention, or a componentthereof, is being manipulated—for instance, physically transferred—inconjunction with their employment for a process of the invention. Inthis regard, use conditions include the conditions under which therelease agent or component is depleted from its sump, or storage area,as well as conditions in the electrostatographic reproduction apparatusand system during operation, particularly fusing process conditions, andconditions under which the release agent or component is being appliedto the toner and/or substrate surface.

Organomers include hydrocarbons and perhalopolyethers, and organomerblocks correspondingly include hydrocarbyl blocks and perhalopolyetherblocks. The preferred perhalopolyethers are the perfluoropolyethers.

The term “halo” as used herein includes chloro, bromo, iodo, and fluoro.

Unless stated otherwise, molecular weights set forth herein are numberaverage molecular weights (M_(n)), measured in Daltons.

The polarity value of a group—i.e., a group of two or more covalentlybonded atoms—is determined using modified Hansen dispersion, polar, andhydrogen bonding parameters for the group. These modified Hansenparameters are calculated using the procedure for calculating Hansenparameters from the Hansen group contribution values—with a variation tothis procedure.

The Hansen parameter calculation procedure is set forth in Table 16, atpage 185, of the CRC Handbook of Solubility Parameters and OtherCohesion Parameters, Second Edition, Allan F. Barton, Ph.D. (1991); thishandbook is incorporated herein in its entirety, by reference thereto.The indicated variation to this procedure is that the group molarvolume, employed for calculating all three parameters, is determinedusing 0.85 g/cm³ as the density value.

As for the modified Hansen parameters calculated according to theforegoing procedure, the modified polar parameter and the modifiedhydrogen bonding parameter are added together, and the sum of these twoparameters is divided by the modified dispersion parameter. The resultis the polarity value.

A polymer of the invention comprises at least one polyorganosiloxaneblock, at least one organomer block, and at least one group, orlinkage—particularly, at least one polar group, or polarlinkage—covalently bonding a polyorganosiloxane block and an organomerblock. The at least one organomer block comprises at least one memberselected from the group consisting of hydrocarbyl blocks andperhalopolyether blocks.

Each polar linkage includes a group, or functionality—particularly, apolar group, or polar functionality—that has a polarity value of atleast about 1.8, more preferably of at least about 2, and still morepreferably of at least about 2.6. Specifically, polar functionalities ofthe invention have polarity values of at least about 1.8, morepreferably of at least about 2, and still more preferably of at leastabout 2.6.

The polarity value of a polar functionality is determined by finding,within the functionality, the group of connected atoms that itself hasthe highest polarity value, and also comprises at least three atoms,with at least one of these three atoms being a carbon atom; this groupmay be made up of a part, or all, of the atoms of the polarfunctionality. The polarity value of this group is the polarity value ofthe polar functionality.

Preferably the polar functionality comprises a hydrogen atom that ishydrogen bondable (i.e., a hydrogen bondable H atom). A polar linkagecan consist of, or consist essentially of, or consist substantially of,the polar functionality as discussed, or it can further include one ormore substituents in addition to the polar functionality.

Each—or at least essentially each, or at least substantiallyeach—polyorganosiloxane block can be covalently bonded to at least oneorganomer block by a polar linkage, and/or each—or at least essentiallyeach, or at least substantially each—organomer block can be covalentlybonded to at least one polyorganosiloxane block by a polar linkage. As amatter of particular preference, each, or at least essentially each, orat least substantially each, connection between a polyorganosiloxaneblock and an organomer block comprises a polar linkage covalentlybonding these blocks.

The polymers of the invention can be referred to as blockpolyorganosiloxane block organomer polymers. Polymers of the inventioninclude graft polymers and block polymers. A polymer of the inventionmay be in a linear configuration and/or in a branched configuration.

A linear configuration can comprise alternating linearpolyorganosiloxane and organomer blocks—one or more of each—sequentiallyconnected at their block ends. With respect to the foregoing, a blockend comprises a terminal siloxy unit, C atom, or perhalocarboxy unit ofthe polyorganosiloxane block, hydrocarbyl block, perhalopolyether block,respectively.

A branched configuration can comprise at least one linearpolyorganosiloxane block connected to one or more linear organomerblocks along the polyorganosiloxane block, with at least onepolyorganosiloxane block/organomer block connection being at a siloxyunit of the polyorganosiloxane block which is not a terminal siloxy unitthereof (i.e., which is a nonterminal siloxy unit thereof); and/or, atleast one linear organomer block connected to one or more linearpolyorganosiloxane blocks along the organomer block, with at least onepolyorganosiloxane block/organomer block connection being at a C atom(perhalocarboxy unit) of the hydrocarbyl (perhalopolyether) block whichis a nonterminal C atom (perhalocarboxy unit) thereof. The at least onepolyorganosiloxane block/organomer block connection may be between aterminal unit (C atom) of one and a nonterminal unit (C atom) of theother, or between nonterminalities of both—i.e., between apolyorganosiloxane nonterminal siloxy unit and a perhalopolyethernonterminal perhalocarboxy unit, or between a polyorganosiloxanenonterminal siloxy unit and a hydrocarbyl nonterminal C atom.

Polymers of the invention include diblock polymers, triblock polymers,etc. Preferred polymers of the invention are diblock polymers of onepolyorganosiloxane block and one organomer block, triblock polymers oftwo polyorganosiloxane blocks and one organomer block, and triblockpolymers of two organomer blocks and one polyorganosiloxane block. Ofthese, linear and branched diblock polymers, and linear and branchedtriblock polymers, are particularly preferred, with the linear andbranched diblock polymers being the most preferred.

Preferably the polymers of the invention have a molecular weight ofabout 3,000 or greater. More preferably, polymers of the invention havea molecular weight of from about 4,000 to about 250,000, and still morepreferably of from about 6,000 to about 100,000.

Regarding polar linkages, and particularly as to polar functionalities,among these functionalities are secondary amine groups, hydroxyl groups,and phenolic groups. Preferably for the present invention, the polarfunctionality comprises, as discussed, a hydrogen bondable H atom.

Also as a matter of preference, the polar functionality comprises both ahydrogen bond donor, or donating group—i.e., a group that provides thehydrogen bondable H atom—and also a hydrogen bond acceptor, or acceptinggroup. As indicated, the hydrogen bond donating and accepting groups areseparate and different entities—i.e., they do not have any atoms incommon; both groups are part of the polar functionality. Yetadditionally as a matter of preference, the hydrogen bond donors andacceptors are adjacent, with an atom of one group covalently bonded toan atom of the other.

A suitable hydrogen bond donor is —NH—. A suitable hydrogen bondacceptor is the carbonyl group,

Preferred polar functionalities that include both a hydrogen bond donorand a hydrogen bond acceptor are amide incorporating groups—i.e., groupsincorporating the amide configuration. An amide incorporating groupwhich may be used is the amide group itself—i.e.,

Additional suitable amide incorporating groups are the urea group—i.e.,

and the urethane group, i.e.,

An advantage of the amide incorporating polar functionalities is thatthe —NH— hydrogen bonding is enhanced by the amide configuration.Particularly, the

group activates the —NH— group, thereby causing the polar functionalityto provide stronger hydrogen bonding.

As to the foregoing three particular polar functionalities, the polarityvalue for the amide group is determined from the entire amide group,while for the urea group either of the amide configurations within thegroup can be used, and for the urethane group also the incorporatedamide configuration is used. Each of these three polar functionalitieshas a polarity value of about 2.8.

Polymers of the invention are prepared from polyorganosiloxane andorganomer precursors of the corresponding polyorganosiloxane andorganomer blocks. Polyorganosiloxanes, hydrocarbons, andperhalopolyethers that may be used as precursors for the presentinvention may be prepared in accordance with processes as are known inthe art. Suitable polyorganosiloxane, hydrocarbon, and perhalopolyetherprecursors include polyorganosiloxane, hydrocarbon, and perhalopolyetherpolymers, oligomers, and macromers.

A polyorganosiloxane precursor of the invention comprises apolyorganosiloxane having at least one polar linkage forming group, ormoiety—i.e., having one of these groups, or moieties, or having two ormore of these groups, or moieties. Correspondingly, an organomerprecursor of the invention comprises an organomer having at least onepolar linkage forming group, or moiety—i.e., having one of these groups,or moieties, or having two or more of these groups, or moieties.

Polar linkage forming moieties include functional groups that react toform the polar functionalities; these functional groups can be referredto as polar functionality forming groups. A polar linkage forming moietycan consist of, or consist essentially of, or consist substantially of,a polar functionality forming group as indicated, or it can furtherinclude one or more substituents in addition to the polar functionalityforming group.

The polar linkage forming moieties and polar functionality forminggroups, of the polyorganosiloxane precursors, can be referred to asfirst polar linkage forming moieties and first polar functionalityforming groups, respectively. Correspondingly, the polar linkage formingmoieties and polar functionality forming groups, of the organomerprecursors, can be referred to as second polar linkage forming moietiesand second polar functionality forming groups, respectively.

The polar linkage of the invention is obtained from the reaction betweena polar linkage forming moiety of a polyorganosiloxane precursor, and apolar linkage forming moiety of an organomer precursor—i.e., between afirst polar linkage forming moiety and a second polar linkage formingmoiety. Specifically, the polar functionality forming groups of therespective polar linkage forming moieties (i.e., first and second polarfunctionality forming groups)—react to provide the polar functionality.

Polyorganosiloxane blocks of the invention, which can also be referredto as release blocks, include linear blocks and branched blocks.Preferred polyorganosiloxane blocks are polydimethylsiloxaneblocks—i.e., derived from the corresponding polydimethylsiloxaneprecursors.

The polyorganosiloxane blocks of the present invention includehomopolymer blocks and copolymer blocks of dimethylsiloxane,diphenylsiloxane, methyl-3,3,3-trifluoropropylsiloxane, andmethylphenylsiloxane monomeric units. Preferred polyorganosiloxaneblocks include polydimethylsiloxane, polyphenylmethylsiloxane,polydiphenylsiloxane, poly(diphenyl-co-dimethyl)siloxane, andpoly(phenylmethyl-co-diphenyl)siloxane, with polydimethylsiloxane beingmost preferred.

Polyorganosiloxane blocks and precursors of the invention preferablyhave a molecular weight of from about 2,000 to about 250,000. Morepreferably, polyorganosiloxane blocks and precursors of the inventionhave a molecular weight of from about 4,000 to about 120,000, and stillmore preferably of from about 6,000 to about 80,000.

Suitable polyorganosiloxane precursors include linear polyorganosiloxaneprecursors having one polar linkage forming moiety, and linearpolyorganosiloxane precursors having two or more polar linkage formingmoieties. Branched polyorganosiloxane precursors having one polarlinkage forming moiety, and branched polyorganosiloxane precursorshaving two or more polar linkage forming moieties, also may be used.

It is preferred that the covalent linkage, to the polyorganosiloxaneblock, be stabilized against intramolecular reaction. A means forachieving this objective is to utilize a polar linkage forming moietywhich separates the polar functionality forming group from thepolyorganosiloxane block by at least three carbon atoms, andparticularly by at least three methylene units—especially in the case ofcarboxyl polar functionality forming groups, and in the case of primaryamine polar functionality forming groups, and with halo (particularlyfluoro) functional groups as well.

Accordingly, preferred polar linkage forming moieties for thepolyorganosiloxane precursors comprise C₃ and greater hydrocarbyl spacergroups, and particularly C₃ and greater alkyl spacer groups, connectingthe polar functionality forming groups to the polyorganosiloxane blocks.Of these, the n-alkyl spacer groups are especially preferred, with then-propyl spacer group being most preferred.

Among the linear polyorganosiloxane precursors that may be used arethose with one or more pendant or side polar linkage forming moietiesand/or one or more terminating polar linkage forming moieties. In thisregard, it is understood that pendant, or side, polar linkage formingmoieties are attached along the polyorganosiloxane backbone, tononterminal siloxy units, and that terminating polarlinkage formingmoieties are attached on the polyorgano-siloxane backbone, to terminalsiloxy units.

Further as to linear polyorganosiloxane precursors, those that may beused for providing the polyorganosiloxane blocks include linearpolyorganosiloxanes having a single polar linkage forming moiety whichis a terminating moiety—i.e., with this polar linkage forming moietyattached to one terminal siloxy unit of the correspondingpolyorganosiloxane block, and thereby terminating one end of the linearprecursor. Also suitable as precursors are linear polyorganosiloxaneswith two polar linkage forming moieties, both of which are terminatingmoieties—i.e., having one of the polar linkage forming moieties attachedat either terminal siloxy unit of the corresponding polyorganosiloxaneblock, and thereby terminating both ends of the linear precursor.

Yet additionally as to linear polyorganosiloxane precursors, those thatmay be used include precursors having the formulaX_(c)-[(D¹)_(a)-ran-(D²)_(b)]-X_(d)wherein

-   -   R¹, R², and R³ are the same or different, and are selected from        the group consisting of C₁-C₁₀ hydrocarbyl groups;    -   X is a polar linkage forming moiety;    -   a is 40 to 2500;    -   b is 0 to 4;    -   c is 0 or 1;    -   d is 0 or 1; and    -   b+c+d is 1 to 4.

Preferably R¹, R², and R³ are methyl groups, a is 60 to 2000, b is 0 to1, and b+c+d is 1 or 2.

Branched polyorganosiloxane precursors that may be used include thosehaving the formulaX-(D³)_(e)-[(D⁴)_(f)-ran-(T)_(g)];and being endcapped by

wherein

-   -   X-(D³)_(e) is a linear moiety;    -   [(D⁴)_(f)-ran-(T)_(g)] is a branched moiety;    -   R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ are the same or different,        and are selected from the group consisting of C₁-C₁₀ hydrocarbyl        groups;    -   X is a polar linkage forming moiety;    -   T is (R¹¹)_(h)SiO_((4-h)/2);    -   e is 1 to 300;    -   f is 25 to 5000;    -   g is 2 to 100; and    -   h is 0 or 1.

Branched polysiloxanes, particularly monofunctional branchedpolysiloxanes, disclosed in U.S. Provisional Application No. 60/305,874,filed Jul. 18, 2001, are suitable branched polyorganosiloxane precursorsfor the present invention. Further, the process disclosed therein forpreparing branched polysiloxanes are suitable for preparing branchedpolyorganosiloxane precursors for the present invention.

Hydrocarbyl blocks of the invention include linear blocks and branchedblocks. Preferred hydrocarbyl blocks are nonsubstituted hydrocarbylblocks—particularly, consisting or consisting essentially of carbon andhydrogen atoms, and derived from the corresponding nonsubstitutedhydrocarbon precursors—with alkyl blocks, such as lauryl and stearylgroups, being particularly preferred. Also preferred are nonhalogenatedhydrocarbyl blocks, especially nonhalogenated alkyl blocks, andnonfluorinated hydrocarbyl blocks, especially nonfluorinated alkylblocks, are particularly preferred—particularly, here also, blocksderived from the corresponding hydrocarbon precursors.

Suitable hydrocarbon precursors of the invention, and accordingly thehydrocarbyl blocks derived therefrom, include hydrocarbon waxes andoils. These include hydrocarbons that are oils at 25° C., and stillliquid at operating temperatures, particularly fusing processtemperatures, and hydrocarbons that are waxes at 25° C., but liquid atoperating temperatures, particularly fusing process temperatures.

Among the hydrocarbyl blocks and hydrocarbon precursors which can beused are hydrocarbyl blocks, such as hydrocarbyl chains, and hydrocarbonprecursors, such as hydrocarbon precursor chains, comprising at leastabout 8 C atoms, more preferably at least about 16 C atoms, still morepreferably at least about 22 C atoms, still more preferably at leastabout 30 C atoms, still more preferably about 40 C atoms, or at leastabout 40 C atoms, and still more preferably at least about 50 C atoms.Also among the hydrocarbyl blocks and hydrocarbon precursors which canbe used are hydrocarbyl blocks, such as hydrocarbyl chains, andhydrocarbon precursors, such as hydrocarbon precursor chains, comprisingfrom about 8 to about 600 C atoms, more preferably from about 16 toabout 500 C atoms, still more preferably from about 22 to about 400 Catoms, still more preferably from about 30 to about 400 C atoms, andstill more preferably from about 40 to about 200 C atoms. Thehydrocarbon precursors, and the corresponding hydrocarbyl blocks, may besubject to minor modification, such as a small degree of, or slight,oxidation.

Particular hydrocarbyl blocks which are suitable are polyethyleneblocks. Polyethylene blocks and precursors of the invention preferablyhave a molecular weight of from about 300 to about 10,000.

Halocarbyl (especially haloalkyl) blocks also are suitable hydrocarbylblocks of the invention. Preferred haloalkyl blocks are the perhaloalkylblocks, especially the perfluoroalkyl blocks, such as theperfluorodecanyl and perfluorotetradecanyl groups.

Particularly as to fluorocarbyl blocks, the presence of these improvesthe wetting—by polymers of the invention—of fuser member surfaces whichthemselves are fluorinated, or include fluorine substituents, asdiscussed. Examples of these surfaces are those comprisingpolyfluorocarbons. Suitable polyfluorocarbons include fluoroelastomers.Also included are nonelastomeric fluorocarbon materials, such asfluoroplastics and fluororesins, like polytetrafluoroethylene (PTFE),and copolymers of tetrafluoroethylene (TFE) and perfluoroalkylvinylether(PFA), and fluorinated ethylene propylene copolymers. However,fluorocarbon precursors and their corresponding blocks are characterizedby higher surface activity, and the precursors have relatively lowercompatibility, particularly with polyorganosiloxanes. For this reason,preferably the fluorocarbyl blocks are somewhat smaller in size.

In this regard, the halocarbyl blocks and halocarbon precursors, such asperhaloalkyl blocks and perhaloalkane precursors, preferably comprisefrom about 4 to about 50 C atoms. More preferably, the halocarbyl blocksand halocarbon precursors, such as perhaloalkyl blocks and perhaloalkaneprecursors, comprise from about 6 to about 30 C atoms; still morepreferably, from about 8 to about 20 C atoms.

Particularly as to the perfluoroalkyl blocks, those comprising an evennumber of carbon atoms are simple irritants. However, there areperfluoroalkyl blocks with odd numbers of carbon atoms that are known tobe toxic. Accordingly, the even number blocks are preferred.

Preferably, the hydrocarbon precursors are low vapor pressure, nontoxic,nonsensitizing molecules. Suitable hydrocarbon precursors include linearhydrocarbon precursors having one polar linkage forming moiety, andlinear hydrocarbon precursors having two or more polar linkage formingmoieties. Branched hydrocarbon precursors having one polar linkageforming moiety, and branched hydrocarbon precursors having two or morepolar linkage forming moieties, also may be used.

Among the linear hydrocarbon precursors that may be used are those withone or more pendant or side polar linkage forming moieties and/or one ormore terminating polar linkage forming moieties. In this regard, it isunderstood that pendant, or side, polar linkage forming moieties areattached along the hydrocarbon backbone, to nonterminal C atoms, andthat terminating polar linkage forming moieties are attached on thehydrocarbon backbone, to terminal C atoms.

Further as to linear hydrocarbon precursors, those that may be used forproviding the hydrocarbyl blocks include linear hydrocarbons having asingle polar linkage forming moiety which is a terminating moiety—i.e.,with this polar linkage forming moiety attached to one terminal C atomof the corresponding hydrocarbyl block, and thereby terminating one endof the linear precursor. Also suitable as precursors are linearhydrocarbons with two polar linkage forming moieties, both of which areterminating moieties—i.e., having one of the terminating polar linkageforming moieties attached at either terminal C atom of the correspondinghydrocarbyl block, and thereby terminating both ends of the linearprecursor.

As to polyethylene precursors in particular, suitable examples includethose which are solid at 25° C., but liquid at operating temperatures,particularly fusing process temperatures.

A commercially available hydrocarbon suitable for use as a precursor isUnicid® 700, a carboxy functional hydrocarbon from Baker Petrolite, SandSprings, Okla.

Perhalopolyether blocks of the invention include linear blocks andbranched blocks. Perhalopolyether blocks include homopolymer blocks andcopolymer blocks of perhalocarboxy monomeric units.

Suitable perhalocarboxy monomeric units include C₁ and greaterperhalocarboxy monomeric units, especially C₁ and greater perhaloalkoxymonomeric units, with the C₁-C₁₀ perhalocarboxy monomeric units, andespecially the C₁-C₁₀ perhaloalkoxy monomeric units, being particularlypreferred. Particular monomeric units that may be used include theperfluoromethoxy (—OCF₂—), perfluoroethoxy (—OCF₂CF₂—), perfluoropropoxy(—OCF₂CF₂CF₂—), perfluoroisopropoxy (—OCF(CF₃) CF₂—), perfluorobutoxy(—OCF₂CF₂CF₂CF₂—), perfluorosecbutoxy (—OCF(CF₃) CF₂CF₂—), andperfluoroisobutoxy (—OCF₂C(CF₃)₂—) monomeric units.

Like the indicated fluorocarbyl blocks, perfluoropolyether blocksimprove the wetting—by polymers of the invention—of fuser membersurfaces which themselves include fluorine substituents.

Perhalopolyether blocks and precursors of the invention preferably havea molecular weight of from about 200 to about 12,000. More preferably,perhalopolyether blocks and precursors of the invention have a molecularweight of from about 400 to about 8,000, and still more preferably offrom about 600 to about 4,000.

Suitable perhalopolyether precursors include linear perhalopolyetherprecursors having one or two polar linkage forming moieties. Branchedperhalopolyether precursors having one polar linkage forming moiety, andbranched perhalopolyether precursors having two or more polar linkageforming moieties, also may be used.

Particularly as to linear perhalopolyether precursors, those that may beused include linear perhalopolyethers having a single polar linkageforming moiety which is a terminating moiety—i.e., with this polarlinkage forming moiety attached to one terminal perhalocarboxy unit ofthe corresponding perhalopolyether block, and thereby terminating oneend of the linear precursor. Also suitable as precursors are linearperhalopolyethers with two polar linkage forming moieties, both of whichare terminating moieties—i.e., having one of the terminating polarlinkage forming moieties attached at either terminal perhalocarboxy unitof the corresponding perhalopolyether block, and thereby terminatingboth ends of the linear precursor.

As to the foregoing, terminating moieties preferably are attachedparticularly to terminal C atoms of perhalopolyether blocks—e.g., toperhalomethylene, particularly (—CF₂—), units. Further, terminalperhalocarboxy units that do not have attached polar linkage formingmoieties can have suitable endcaps, or attached terminal groups. Amongthe groups suitable for this purpose are perhalomethyl, particularly(—CF₃), groups.

Commercially available perfluoropolyethers that are suitable precursorsinclude the following, all from Ausimont USA, Inc., Thorofare, N.J.:Fomblin® Z-Diac, which is a dicarboxy functional perfluoropolyether,having two carboxyl groups, one terminating each end of theperfluoropolyether; Fomblin® MF-300, which is a monocarboxy functionalperfluoropolyether, with a single carboxyl group terminating one end ofthe perfluoropolyether; and Fomblin® Z-Diol, which is a dihydroxyfunctional perfluoropolyether, having two hydroxyl groups, oneterminating each end of the perfluoropolyether.

The totality of the polyorganosiloxane blocks—i.e., the one or morepolyorganosiloxane blocks—of the polymer of the invention, is referredto as the polyorganosiloxane component of the polymer. Correspondingly,the totality of the organomer blocks is referred to as the organomercomponent.

The organomer component can be a hydrocarbyl component—i.e., with all ofthe one or more organomer blocks being hydrocarbyl blocks—or it can be aperhalopolyether component—i.e., with all of the one or more organomerblocks being perhalopolyether blocks—or it can include both one or morehydrocarbyl blocks and one or more perhalopolyether blocks.

The polymer of the invention accordingly can comprise a hydrocarbylcomponent and/or a perhalopolyether component. And, for instance, thehydrocarbyl component can comprise a halocarbyl component.

Discussion concerning organomer components applies to hydrocarbylcomponents and to perhalopolyether components.

Preferably the polyorganosiloxane component has a greater molecularweight than the organomer component. In this regard, thepolyorganosiloxane component can be in the form of a singlepolyorganosiloxane block having a molecular weight greater than that ofa single organomer block or the sum of multiple organomer blockmolecular weights, or the polyorganosiloxane component can be in theform of multiple polyorganosiloxane blocks having a total molecularweight greater than that of a single organomer block or the sum ofmultiple organomer block molecular weights.

Also as a matter of preference, the polyorganosiloxane componentcomprises a majority of the polymer of the invention. Here, a majoritymeans that the molecular weight of the polyorganosiloxane componentcomprises more than 50 percent of the molecular weight of the polymer.

As a matter of particular preference, the polymer of the invention ispredominantly polyorganosiloxane—i.e., the polyorganosiloxane componentis predominant. This predominance refers to the molecular weight of thepolyorganosiloxane component comprising at least 75 percent of themolecular weight of the polymer.

As to the relative sizes of the polyorganosiloxane and organomer blocksin a polymer of the invention, preferably the polyorganosiloxane blockmolecular weight is greater than the organomer block molecular weight.In the case of hydrocarbyl blocks, the mole ratio of polyorganosiloxaneblock Si atoms to hydrocarbyl block C atoms preferably is greater thanabout 1:3; this ratio more preferably is from about 1:1 to about 40:1,still more preferably from about 1:1.5 to about 30:1, and still morepreferably from about 2:1 to about 20:1—particularly in the case ofpolydimethylsiloxane blocks (i.e., with dimethylsiloxy units) and alkylblocks (i.e., having methylene units).

Further as to this matter, particularly in the case of halocarbylblocks, and most especially fluorocarbyl blocks, the mole ratiopreferably is greater than about 1:1; this ratio more preferably is fromabout 1:1 to about 40:1, still more preferably from about 2:1 to about140:1, and still more preferably from about 3:1 to about 100:1, andstill more preferably from about 4:1 to about 70:1. And particularly inthe case of perhalopolyether blocks, and most especiallyperfluoropolyether blocks, the mole ratio of polyorganosiloxane block Siatoms to perhalopolyether block C atoms preferably is greater than about1:3; this ratio more preferably is from about 1:1 to about 140:1, stillmore preferably from about 1.5:1 to about 100:1, and still morepreferably from about 2:1 to about 70:1.

Additionally in the case particularly of polydimethylsiloxane and alkylblocks, preferably the polydimethylsiloxane block to alkyl blockmolecular weight ratio is from about 5:1 to about 400:1, more preferablyfrom about 8:1 to about 100:1, still more preferably from about 12:1 toabout 55:1, still more preferably from about 15:1 to about 30:1.Particularly with polydimethylsiloxane and fluoroalkyl blocks,preferably the polydimethylsiloxane block to fluoroalkyl block molecularweight ratio is from about 5:1 to about 400:1, more preferably fromabout 7:1 to about 150:1, still more preferably from about 9:1 to about75:1, still more preferably from about 11:1 to about 40:1.

As to using polymers of the invention—particularly, using these polymersin toner fusing processes—it is believed that the polyorganosiloxaneblocks, the hydrocarbyl blocks, the perhalopolyether blocks, and thepolar functionalities thereof all have advantageous effects, infacilitating the combating of toner offset and toner buildup on fusermembers.

In this regard, the hydrocarbyl blocks are thought to exhibitsurfactant-like behavior, and to interact with nonpolar surfaces, likethe fusing process toner. Waxy hydrocarbyl blocks, by virtue of theirwaxy nature, lubricate toner, and allow it to peel from surfaces withoutoffset.

The polyorganosiloxane blocks likewise are thought to exhibitsurfactant-like behavior. Where polymer of the invention is employedwith polyorganosiloxane release agent—e.g., as part of a release agentcomposition—the polyorganosiloxane blocks are further thought to promotewetting of the surfaces by the release agent.

This is particularly the case where polyorganosiloxane release agent, asdiscussed, comprises about 50 percent by weight or more, and even 75percent by weight or more, of the composition. In such instance, evenwhere polymer of the invention comprises a comparatively minor portionby weight of the release agent composition, it promotes wetting of fusermember surfaces by the composition; and this is especially the casewhere the organomer component—of the polymer of the invention—comprisesa fluorocarbyl block and/or a perfluoropolyether block, and mostespecially where, yet additionally, the fuser member surface to whichthe composition is applied is fluorinated, or includes fluorinesubstituents—e.g., comprises polyfluorocarbon, or is provided by apolyfluorocarbon fusing surface layer. With respect to the foregoing,silicones—polyorganosiloxanes—are known in the art to be particularlyuseful as release agents, and the polyorganosiloxane block furtherpromotes release of the toner from surfaces without offset.

And yet additionally with regard to employing the polymer of theinvention—as indicated—with polyorganosiloxane release agent, and withthe organomer component comprising a fluorocarbon and/orperfluoropolyether block or blocks, the polyorganosiloxane block orblocks, by their covalent bonding with the fluorine-containing organomercomponent, stabilize this component. In this regard, ordinarilyfluorine-containing materials do not blend or mix well withnonfluorine-containing materials. However, because of thisstabilization, separation of the fluorocarbon and/or perfluoropolyetherfrom the composition is minimized.

The polar functionalities are thought to interact with polar sites, orhigh energy sites, on the toner and/or on the fuser member. These sitesinclude exposed fusing surface layer fillers, like metal oxides, andcontaminants, such as paper debris. Because the polar functionality isat the linkage between the polyorganosiloxane and organomer blocks,either type of block may bring it to a surface to attach to a polar orhigh energy site, and participate in shielding the site. Thepolyorganosiloxane and organomer blocks serve to effect coating, andprevent adhesion to other surfaces.

A block polyorganosiloxane block organomer polymer of the invention canbe prepared by reacting together at least one polyorganosiloxaneprecursor and at least one organomer precursor. In the reaction ofpolyorganosiloxane and organomer precursors, first and second polarlinkage forming moieties form polar linkages, and first and second polarfunctionality forming groups form polar functionalities, as discussed.

The amide polar functionality can be obtained by reaction of a primaryamine polar functionality forming group (i.e., —NH₂)—particularly anamidization reactive primary amine polar functionality forminggroup—with a carboxyl or acid chloride polar functionality forming group(i.e., —COOH or —COOCl)—particularly an amidization reactive carboxyl oracid chloride polar functionality forming group. Accordingly, the firstpolar linkage forming moieties (i.e., the polyorganosiloxane precursormoieties) can comprise one of primary amino functional groups andcarboxy functional groups, and the second polar linkage forming moieties(i.e., the organomer precursor moieties) can comprise the other. Or thefirst polar linkage forming moieties (i.e., the polyorganosiloxaneprecursor moieties) can comprise one of primary amino functional groupsand acid chloride functional groups, and the second polar linkageforming moieties (i.e., the organomer precursor moieties) can comprisethe other.

Therefore, as one possibility, a primary amino functionalpolyorganosiloxane and a carboxy functional organomer can be reacted toprovide a block polyorganosiloxane block organomer polymer of theinvention. Other possible combinations that can be utilized for thisreaction are: primary amino functional polyorganosiloxane/acid chloridefunctional organomer; carboxy functional polyorganosiloxane/primaryamino functional organomer; and acid chloride functionalpolyorganosiloxane/primary amino functional organomer.

The foregoing also applies to reacting a primary amine polarfunctionality forming group with an isocyanate polar functionalityforming group (i.e., —N═C═O) to provide the urea polar functionality,and to reacting a hydroxyl polar functionality forming group (i.e., —OH)with an isocyanate polar functionality forming group to provide theurethane polar functionality.

In a method of preparing amide polar functionality polymers of theinvention—from primary amino functional and carboxy or acid chloridefunctional polyorganosiloxanes and organomers, such as hydrocarbons,including fluorocarbons, and perfluoropolyethers—the precursors areadded together, and brought to a temperature sufficient to place all ofthe precursors, both polyorganosiloxane and organomer precursors, in aliquid state. If all of the precursors are liquid at ambienttemperature, then heating is not necessary at this point; otherwise,heating is effected to raise the temperature sufficiently so as to meltall solid precursor or precursors. Once the reactants are in the liquidstate, they are suitably blended, or mixed, preferably to a uniformcomposition.

Particularly where carboxy functional precursors are employed, thetemperature is elevated to the point required for effecting reaction ofthe primary amine and carboxyl functionalities, and for causingformation of the corresponding amide polar functionality by theelimination of water. Specifically, the mixture is brought to atemperature of at least about 80° C., more preferably at least about100° C. Particularly, the reaction temperature is preferably from about100° C. to about 200° C., more preferably from about 110° C. to about175° C., and still more preferably from about 120° C. to about 160° C.

The mixture is maintained at the reaction temperature for a timesufficient to permit the indicated amidization. The amount of timerequired depends on, inter alia, the temperature, and the identity ofthe reactants.

For instance, at reaction times of from about 30 minutes to about 6hours, temperatures of from about 130° C. to about 150° C. are employed.Longer reaction periods may be required for lower temperatures, andshorter periods for higher temperatures.

During reaction at elevated temperatures, preferably the mixture iscontinuously blended or mixed. However, this treatment is not requiredbeyond what is necessary to obtain a uniform composition.

In contrast to carboxy functional precursors, with the acid chloridesthe temperature need only be high enough so that all the precursors arein the liquid state, in order for amidization readily to proceed.However, heating to a higher temperature may be employed to acceleratethe reaction. Particularly, preferably the mixture is heated at atemperature of from about 30° C., or about 60° C., to about 150° C., orabout 200° C. In any event, with acid chloride functional precursors,the indicated mixing of reactants in the liquid state is continued untilthe amidization is complete, or at least essentially complete.

With both carboxy and acid chloride functional precursors, the reactionmay be conducted in the ambient air, such as in an open kettle, or in aclosed system, provided there are means for removing evolved water (inthe case of carboxy functional precursors) or HCl (for acid chloridefunctional precursors). Water or HCl removal may be done with a nitrogensweep, or by vacuum.

Preparing the amide polar functionality polymers, from primary aminofunctional and carboxy or acid chloride functional polyorganosiloxanesand organomers, is comparatively simple, because of the interaction ofthe primary amino functional and carboxy functional groups, and theinteraction of the primary amino functional and acid chloride functionalgroups. In this regard, mixing between the precursors is facilitated bythe miscibility of these groups, thereby enhancing ease of preparation.

And this advantage is of particular value with fluorocarbon andperfluoropolyether precursors. Normally, reacting fluorine containingmaterials with nonfluorine containing materials is difficult, because—asdiscussed—the former do not blend or mix well with the latter.Therefore, to achieve the desired reaction, it is often necessary to useextreme measures, such as employing exotic solvents that will solubilizeboth the fluorine and nonfluorine reactants. However, where it is theindicated NH₂/COOH or NH₂/COOCl functional precursor combinations thatare employed, then because of the indicated interaction and improvedmixing that characterizes the acyl and base functional reactants, theprecursors readily blend together and react—whether the fluorocarbonand/or the perfluoropolyether are acyl or primary amino functional.

Urea polar functionality polymers of the invention can be prepared fromprimary amino functional and isocyanate functional polyorganosiloxanesand organomers, in accordance with recognized synthetic pathways forprimary amine and isocyanate reactants. Likewise, urethane polarfunctionality polymers of the invention can be prepared from hydroxyfunctional and isocyanate functional polyorganosiloxanes and organomers,in accordance with recognized synthetic pathways for hydroxyl andisocyanate reactants.

For both the urea and the urethane polymer preparation, the reactantsare combined, and brought to a temperature sufficient to place all theprecursors in a liquid state. If all of the precursors are liquid atambient temperature, then heating is not necessary; otherwise, heatingis effected to raise the temperature sufficiently so as to melt allsolid precursor or precursors. Once the reactants are in the liquidstate, they are suitably blended, or mixed.

As where acid chloride precursors are used for preparing the amidefunctional polymers, the reaction will occur where the temperature ishigh enough so that the precursors are all in the liquid state. However,here too heating to higher temperatures may be used to accelerate thereaction. Preferably both urea and urethane preparation are conducted attemperatures of from about 30° C. to about 150° C. Mixing of the liquidstate reactants is continued until the reaction is complete, or at leastessentially complete.

In preparing the urea polar functionality polymer, it may be necessaryto take precautions for removal of water to prevent loss of theisocyanate functionality—for instance, by purging with dry air ornitrogen. Precautions for the removal of water may also be necessary forurethane polymer preparation.

Yet additionally, a catalyst may be employed in both urea and urethanepolymer preparation. A suitable catalyst for each of thesepolymerizations is triethylenediamine.

Particularly with respect to polar linkage forming moieties, those thathave amidization reactive primary amine groups, as their polarfunctionality forming groups, can be characterized as primary aminofunctional polar linkage forming moieties. Correspondingly, polarlinkage forming moieties that have amidization reactive carboxylgroups—or acid chloride groups, or hydroxyl groups, or isocyanategroups—as their polar functionality forming groups, can be characterizedas carboxy functional—or acid chloride functional, or hydroxyfunctional, or isocyanate functional—polar linkage forming moieties.

Suitable primary amino functional—and carboxy functional, and acidchloride functional, and hydroxy functional, and isocyanatefunctional—polar linkage forming moieties include primaryaminohydrocarbyl—and carboxyhydrocarbyl, and acylchlorohydrocarbyl, andhydroxyhydrocarbyl, and isocyanatehydrocarbyl—groups, especially theprimary aminoalkyl—and carboxyalkyl, and acylchloroalkyl, andhydroxyalkyl, and isocyanatealkyl—groups. As to these, the primaryamino—and carboxy, and acid chloride, and hydroxy, and isocyanate—C₁ andgreater hydrocarbyl groups, and especially the primary amino—andcarboxy, and acid chloride, and hydroxy, and isocyanate—C₁ and greateralkyl groups, are preferred, with the primary amino—and carboxy, andacid chloride, and hydroxy, and isocyanate—C₁-C₁₀ hydrocarbyl groups,and especially the primary amino—and carboxy, and acid chloride, andhydroxy, and isocyanate—C₁-C₁₀ alkyl groups, being particularlypreferred, and the primary amino—and carboxy, and acid chloride, andhydroxy, and isocyanate—C₁ and greater n-alkyl groups, especially3-aminopropyl (H₂NCH₂CH₂CH₂—)—and 3-carboxypropyl (HOOC—CH₂CH₂CH₂—), and3-acylchloropropyl (ClOOCCH₂CH₂CH₂—), and 3-hydroxypropyl(HOCH₂CH₂CH₂—), and 3-isocyanatepropyl (OCN—CH₂CH₂CH₂—)—being mostpreferred.

And regarding the polyorganosiloxane precursors in particular,preferably their polar linkage forming moieties have at least threecarbon atoms—especially, three methylene units—separating the polarfunctionality forming group from the polyorganosiloxane block.Accordingly, as to the first polar linkage forming moieties of theinvention, preferred primary amino—and carboxy, and acid chloride, andhydroxy, and isocyanate—functional moieties are the primary amino—andcarboxy, and acid chloride, and hydroxy, and isocyanate—C₃ and greaterhydrocarbyl groups, and especially the primary amino—and carboxy, andacid chloride, and hydroxy, and isocyanate—C₃ and greater alkyl groups,with the primary amino—and carboxy, and acid chloride, and hydroxy, andisocyanate—C₃-C₁₀ hydrocarbyl groups, and especially the primaryamino—and carboxy, and acid chloride, and hydroxy, andisocyanate—C₃-C₁₀alkyl groups, being particularly preferred, and theprimary amino—and carboxy, and acid chloride, and hydroxy, andisocyanate—C₃ and greater (such as C₃-C₁₀) n-alkyl groups, especially3-aminopropyl (H₂NCH₂CH₂CH₂—)—and 3-carboxypropyl (HOOC—CH₂CH₂CH₂—), and3-acylchloropropyl (ClOOC—CH₂CH₂CH₂—), and 3-hydroxypropyl(HOCH₂CH₂CH₂—), and 3-isocyanatepropyl (OCNCH₂CH₂CH₂—)—being mostpreferred.

Additional preferred first polar linkage forming moieties, particularlyfor the branched polyorganosiloxane precursors having the formulaX-(D³)_(e)-[(D⁴)_(f)-ran-(T)_(g)], as discussed herein, are thosecomprising carboxy, as well as acid chloride, and primary amino,functional first moieties having the formula

wherein

-   -   R¹² is selected from the group consisting of the H atom and        C₁-C₁₀ hydrocarbyl groups;    -   R¹³ and R¹⁴ are the same or different, and are selected from the        group consisting of C₁-C₁₀ hydrocarbyl groups;    -   Y is selected from the group consisting H₂N—, ClOOC—, and HOOC—;        and    -   i is 0 to 5.

Functional groups disclosed in U.S. Provisional Application No.60/305,874, and identified therein by the variable X, are suitable asfirst polar linkage forming moieties for the present invention.

Specifically regarding primary amino functional polyorganosiloxanes,polysiloxanes disclosed in U.S. Pat. Nos. 5,489,482, 5,512,409,5,516,361, 5,531,813, and 5,925,779—these patents being incorporatedherein in their entireties, by reference thereto—are suitablepolyorganosiloxane precursors for the present invention. Further, theprocesses disclosed in these patents may be used to preparepolyorganosiloxane precursors for the present invention.

Yet further as to both primary amino functional and carboxy functionalpolyorganosiloxane precursors, polydimethylsiloxanes which may be usedinclude α-aminopropyldimethylsiloxy, ω-trimethylsiloxy terminatedpolydimethylsiloxanes, α,ωaminopropyldimethylsiloxy terminatedpolydimethylsiloxanes, α-carboxypropyldimethylsiloxy, ωtrimethylsiloxyterminated polydimethylsiloxanes, and α,ω-carboxypropyldimethylsiloxyterminated polydimethylsiloxanes. These primary amino functional andcarboxy functional polydimethylsiloxane precursors preferably have amolecular weight of from about 4,000 to about 120,000, more preferablyof from about 6,000 to about 60,000, and still more preferably of fromabout 8,000 to about 40,000. Commercially availablepolydimethylsiloxanes that may be used as precursors include PS513 andPS510 α,ω-aminopropyldimethylsiloxy terminated polydimethylsiloxanes,and PS563 α,ω-carboxypropyldimethylsiloxy terminatedpolydimethylsiloxane, from United Chemical Technologies, Inc., Bristol,Pa.

Further regarding carboxy functional hydrocarbon precursors, those thatare suitable include the fatty acids, such as the C₄-C₃₀, and preferablythe C₁₂-C₂₄ fatty acids. The saturated, monounsaturated, andpolyunsaturated fatty acids may be used, with saturated being preferred.

Particularly as to the saturated, monounsaturated, and polyunsaturatedfatty acids, those with a single carboxyl group at one end of the chainare preferred. Of these, especially preferred are the saturatedmonocarboxylic fatty acids, with the most preferred being those havingthe formulaH₃C(CH₂)_(n)COOHwherein n is 4 to 28.

Also preferred are the saturated, monounsaturated, and polyunsaturatedfatty acids with two carboxyl groups, one at each end of the chain. Ofthese, particularly preferred are the saturated dicarboxylic fattyacids, with the most preferred being those having the formulaHOOC(CH₂)_(n)COOHwherein n is 4 to 28.

Also suitable are the acid chloride forms of the foregoing fatty acids.

Particular fatty acids that may be used include lauric acid, stearicacid, eicosanoic acid, docosanoic acid, tetracosanoic acid, andtricontanoic acid. Particular acid chlorides that may be used are thecorresponding acid chloride forms of these fatty acids.

As to the perfluoroalkanoic, or perfluorocarboxylic acids, the saturatedmonocarboxylic acids, with the single carboxyl group at one end of thechain, are preferred. Particularly preferred are those having theformulaF₃C(CF₂)_(n)COOHwherein n is 4 to 28.

Further preferred of the perfluoroalkanoic acids are the saturateddicarboxylic acids, with one of the two carboxyl groups at each end ofthe chain. Especially preferred are those having the formulaHOOC(CF₂)_(n)COOHwherein n is 4 to 28.

Also suitable are the acid chloride forms of the foregoing theperfluoroalkanoic, or perfluorocarboxylic acids. Particularly preferredare the acid chloride forms of the saturated monocarboxylic acids, withthe single carboxyl group at one end of the chain.

Particular perfluoroalkanoic acids that may be used includeperfluorotetradecanoic acid and perfluorodecanoic acid. Particular acidchlorides that may be used are the corresponding acid chloride forms ofthese perfluoroalkanoic acids.

Further regarding isocyanate functional hydrocarbon precursors, thosethat are suitable include C₄-C₃₀, and preferably the C₁₂-C₂₄ isocyanatefunctional hydrocarbon precursors. The saturated, monounsaturated, andpolyunsaturated isocyanate functional hydrocarbon precursors may beused, with saturated being preferred.

Particularly as to the saturated, monounsaturated, and polyunsaturatedisocyanate functional hydrocarbon precursors, those with a singleisocyanate group at one end of the chain are preferred. Of these,especially preferred are the saturated monoisocyanate hydrocarbons, withthe most preferred being those having the formulaH₃C(CH₂)_(n)NCOwherein n is 4 to 28.

It is advantageous that release agent compositions of the invention befree, or at least essentially free, of free amine groups, particularlyfree primary amine groups. It is correspondingly advantageous that blockpolyorganosiloxane block organomer polymers of the invention be free, orat least essentially free, of free amine groups, particularly freeprimary amine groups.

Further, where primary amino functional precursors are used to preparethe polymers of the invention, it is preferred, when the preparationprocess is complete, that there are no remaining, or at leastessentially no remaining, unreacted primary amino functional polarlinkage forming moieties; there are no remaining, or at leastessentially no remaining, unreacted primary amine polar functionalityforming groups. It is also preferred that the process of preparationleaves no remaining free primary amino functional precursors, or atleast essentially no remaining free primary amino functional precursors.

It is even more advantageous that release agent compositions of theinvention be free, or at least essentially free, of free isocyanategroups. It is correspondingly even more advantageous that blockpolyorganosiloxane block organomer polymers of the invention be free, orat least essentially free, of free isocyanate groups.

Further, where isocyanate functional precursors are used to prepare thepolymers of the invention, it is even more preferred, when thepreparation process is complete, that there are no remaining, or atleast essentially no remaining, unreacted isocyanate functional polarlinkage forming moieties; there are no remaining, or at leastessentially no remaining, unreacted isocyanate polar functionalityforming groups. It is also even more preferred that the process ofpreparation leaves no remaining free isocyanate functional precursors,or at least essentially no remaining free isocyanate functionalprecursors.

Accordingly, where primary amino functional and carboxy or acid chloridefunctional polyorganosiloxane and organomer precursors are used toprepare polymers of the invention, preferably an excess of polarfunctionality forming carboxyl or acid chloride groups, over polarfunctionality forming primary amine groups, is used—particularly,preferably the ratio of carboxy or acid chloride functional polarlinkage forming moieties, to primary amino functional polar linkageforming moieties, is greater than 1:1. As a matter of particularpreference, this ratio is sufficiently greater than 1:1 so that theresulting block polyorganosiloxane block organomer polymer is free, orat least essentially free, of free amine groups, particularly freeprimary amine groups. Also, as a matter of particular preference, theindicated ratio is sufficiently greater than 1:1 so that, when thepreparation process is complete, there are no remaining, or at leastessentially no remaining, unreacted primary amino functional polarlinkage forming moieties. Yet additionally as a matter of particularpreference, the indicated ratio is sufficiently greater than 1:1 so thatthe process of preparation leaves no remaining free primary aminofunctional precursors, or at least essentially no remaining free primaryamino functional precursors.

The discussion concerning the ratio, of carboxy or acid chloridefunctional polar linkage forming moieties to primary amino functionalpolar linkage forming moieties, pertains to the ratio, of carboxyl oracid chloride polar functionality forming groups to primary amine polarfunctionality forming groups.

Correspondingly, where isocyanate functional and hydroxy functionalpolyorganosiloxane and organomer precursors are used to prepare polymersof the invention, preferably an excess of polar functionality forminghydroxyl groups, over polar functionality forming isocyanate groups, isused—particularly, preferably the ratio of hydroxy functional polarlinkage forming moieties, to isocyanate functional polar linkage formingmoieties, is greater than 1:1. As a matter of particular preference,this ratio is sufficiently greater than 1:1 so that the resulting blockpolyorganosiloxane block organomer polymer is free, or at leastessentially free, of free isocyanate groups. Also, as a matter ofparticular preference, the indicated ratio is sufficiently greater than1:1 so that, when the preparation process is complete, there are noremaining, or at least essentially no remaining, unreacted isocyanatefunctional polar linkage forming moieties. Yet additionally as a matterof particular preference, the indicated ratio is sufficiently greaterthan 1:1 so that the process of preparation leaves no remaining freeisocyanate functional precursors, or at least essentially no remainingfree isocyanate functional precursors.

The discussion concerning the ratio, of isocyanate functional polarlinkage forming moieties to hydroxy functional polar linkage formingmoieties, pertains to the ratio, of isocyanate polar functionalityforming groups to hydroxyl polar functionality forming groups.

However, where isocyanate functional and primary amino functionalpolyorganosiloxane and organomer precursors are used to prepare polymersof the invention, ideally the relative proportions of polarfunctionality forming isocyanate and primary amine groups are such that,when the preparation process is complete, there are no remaining, or atleast essentially no remaining, unreacted isocyanate and primary aminofunctional polar linkage forming moieties; there are no remaining, or atleast essentially no remaining, unreacted isocyanate polar functionalityforming groups and primary amine polar functionality forming groups.Also ideally, the relative proportions of polar functionality formingisocyanate and amine groups is such that, when the preparation processis complete, there are no remaining free isocyanate and primary aminofunctional precursors, or at least essentially no remaining freeisocyanate and primary amino functional precursors.

Nevertheless, where this ideal cannot be realized, then becauseunreacted isocyanate remaining after preparation is even less desirablethan unreacted amine, preferably the relative proportions of polarfunctionality forming isocyanate and primary amine groups are such that,when the preparation process is complete, there are no remaining, or atleast essentially no remaining, unreacted isocyanate moieties, and noremaining, or at least essentially no remaining, free isocyanateprecursors, with the amount of unreacted primary amine moieties, and theamount of free primary amine precursors, being minimized.

And where the indicated ideal cannot be realized, then whether or notthe amount of unreacted primary amine moieties and free primary amineprecursors indeed can be minimized, nevertheless preferably the ratio ofprimary amino functional polar linkage forming moieties, to isocyanatefunctional polar linkage forming moieties, is sufficiently greater than1:1, so that the resulting block polyorganosiloxane block organomerpolymer is free, or at least essentially free, of free isocyanategroups. Also, as a matter of preference, the indicated ratio issufficiently greater than 1:1 so that, when the preparation process iscomplete, there are no remaining, or at least essentially no remaining,unreacted isocyanate functional polar linkage forming moieties. Yetadditionally as a matter of particular preference, the indicated ratiois sufficiently greater than 1:1 so that the process of preparationleaves no remaining free isocyanate functional precursors, or at leastessentially no remaining free isocyanate functional precursors.

The discussion concerning the ratio, of primary amino functional polarlinkage forming moieties to isocyanate functional polar linkage formingmoieties, pertains to the ratio, of primary amino polar functionalityforming groups to isocyanate polar functionality forming groups.

Block polyorganosiloxane block organomer polymers of the inventionpreferably have a viscosity of from about 10 cSt to about 200,000 cSt atuse temperatures. Accordingly, a polymer of the invention may be solidat 25° C.—i.e., ambient, or room, temperature—but liquid at the fusingtemperature, or at the temperature of its delivery system duringoperation of the toner fusing system.

Also as a matter of preference, the block polyorganosiloxane blockorganomer polymers of the invention are thermally stable up to atemperature of at least about 120° C.—more preferably of at least about130° C., and still more preferably of at least about 150° C. It isunderstood that thermal stability entails the absence, or at least theessential absence or substantial absence, of degradation, decomposition,and release of byproducts.

The release agent of the invention is, or consists of, or consistsessentially of, or consists substantially of, or comprises, one or moreof the block polyorganosiloxane block organomer polymers of theinvention. In this regard, polymers of the invention have utility asrelease agents or release agent compositions, or as additives, orcomponents, or ingredients—particularly, as active ingredients—inrelease agents or release agent compositions.

Particularly, polymers of the invention can be used neat, or togetherwith one or more other components or ingredients. For example, inaddition to one or more polymers of the invention, the release agentcomposition can comprise one or more release agents, especially one ormore polymeric release agents.

Among the foregoing release agents are polyorganosiloxane releaseagents; polyorganosiloxanes which may be used include those endcapped bytrimethylsiloxy groups. Also suitable are hydrocarbon release agents,particularly polyethylene release agents, and perhalopolyether releaseagents; perhalopolyethers which may be used include those endcapped byperhalomethyl units.

Polymers of the invention comprising a hydrocarbyl component areparticularly suitable for use with hydrocarbon release agents.Correspondingly, polymers of the invention comprising perhalopolyetheror polyorganosiloxane components are particularly suitable for use withperhalopolyether or polyorganosiloxane release agents, respectively.

Hydrocarbon release agents which may be used include polyethylenes, suchas those that are solid at 25° C., but liquid at operating temperatures,particularly fusing process temperatures. Preferred polyethylenes arethose having a molecular weight of from about 300 to about 10,000.

Perhalopolyether release agents which may be used includeperhalopolyether homopolymers and copolymers comprising perhalocarboxymonomeric units as discussed. Perhalopolyethers which may be usedinclude those endcapped by perhalomethyl groups.

Commercially available perfluoropolyethers that are suitable for use asrelease agents include the following: Krytox, from E. I. du Pont deNemours and Company, Deepwater, N.J.; Fomblin® Y45, YR, and YPL1500,from Ausimont USA, Inc.; and Galden® HT230, HT250, HT270, also fromAusimont USA, Inc.

Though perfluoropolyethers as indicated indeed are suitable as releaseagents, their use for this purpose is not preferred, due to costconsiderations. Halocarbons also are not preferred for the same reason,though these are among the hydrocarbons which can be used as releaseagents.

Suitable polyorganosiloxanes include polyorganosiloxane fluids, such asoils and liquids—particularly those that are oils and liquids at 25° C.Polyorganosiloxanes that can be used also include those that are solidat 25° C., but liquid at operating temperatures, particularly fusingprocess temperatures. In this regard, it is understood that the use ofrelease agents that are solid at ambient temperatures but liquid underuse conditions require specialized delivery systems, as are known in theart.

Preferred polyorganosiloxanes are those that are liquid at fusingprocess temperatures, and more preferably have an ambient temperatureviscosity of from about 100 centistokes to about 500 centistokes or toabout 100,000 centistokes, still more preferably from about 350centistokes to about 100,000 centistokes, or from about 500 or 501centistokes to about 70,000 centistokes, or from about 10,000centistokes to about 80,000 centistokes, or from about 10,000centistokes to about 100,000 centistokes, with the viscosity dropping atthe elevated temperatures employed in the fusing process. Wherepolyorganosiloxane viscosity is discussed without indication of whetherthe ambient temperature liquids or solids are intended, then it isunderstood that in the case of the liquids the viscosity is ambienttemperature viscosity, while for solids it is viscosity at operatingtemperatures, particularly fusing process temperatures.

Of the polyorganosiloxanes, the nonfunctional polyorganosiloxanes,particularly the nonfunctional polydimethylsiloxanes, are preferred.Commercially available non-functional polydimethylsiloxanes which may beused are the DC200® polydimethylsiloxanes, from Dow Corning Corporation,Midland, Mich.

Functional polyorganosiloxanes also may be used. One reason foremploying functional polyorganosiloxanes is to enhance interaction ofthe release agent with the fuser member surface, or with material suchas filler incorporated therein.

Particular functional polyorganosiloxanes which may be used includethose disclosed in U.S. Pat. Nos. 4,011,362, 4,046,795, and 4,264,181;these patents also are incorporated herein in their entireties, byreference thereto. Still further functional polyorganosiloxanes whichmay be used are the mercapto functional polyorganosiloxanes, such asthose disclosed in U.S. Pat. No. 4,029,827, and the polyorganosiloxaneshaving functional groups such as carboxy, hydroxy, epoxy, amino,isocyanate, thioether, and (as indicated) mercapto functional groups,such as those disclosed in U.S. Pat. Nos. 4,101,686 and 4,185,140; yetadditionally these patents are incorporated herein in their entireties,by reference thereto.

Suitable functional polyorganosiloxanes include those with one or morependant functional groups and/or one or two terminating functionalgroups—it also being understood that pendant groups are side groups, ormoieties attached along the backbone of the polymer chain, to monomericunits that are not terminal monomeric units of the chain (i.e., that arenonterminal monomeric units thereof), and terminating groups are endgroups, or moieties attached on the backbone of the polymer chain toterminal monomeric units at the polymer chain ends. Particularlypreferred functional polyorganosiloxanes are the monofunctionalpolyorganosiloxanes—these being polyorganosiloxanes having onefunctional group per molecule or polymer chain. Suitable monofunctionalpolyorganosiloxanes include those wherein the sole functional group is aside group; however, the preferred monofunctional polyorganosiloxanesare those which are functional group terminated—i.e., wherein the solefunctional group is at an end of the polymer chain.

The more preferred release agents with functional groups are themercapto functional polyorganosiloxane release agents and the aminofunctional polyorganosiloxane release agents. Particularly preferred arethe release agents, including mecapto functional polyorganosiloxanerelease agents, consisting of, consisting essentially of, consistingsubstantially of, or comprising monomercapto functionalpolyorganosiloxanes, or polyorganosiloxanes having one mercaptofunctional group per molecule or polymer chain. Also particularlypreferred are release agents, including amino functionalpolyorganosiloxane release agents, consisting of, consisting essentiallyof, consisting substantially of, or comprising monoamino functionalpolyorganosiloxanes, or polyorganosiloxanes having one amino functionalgroup per molecule or polymer chain. In this regard, the release agentsdisclosed in U.S. Pat. Nos. 5,531,813 and 6,011,946 may be used; thesepatents are incorporated herein in their entireties, by referencethereto.

The release agent accordingly can comprise, in addition to one or moreblock polyorganosiloxane block organomer polymers of the invention, oneor more non-functional polyorganosiloxanes, and/or one or morefunctional polyorganosiloxanes. The release agent can be a blend ormixture of the indicated components, and can be employed in the form ofa blend or mixture, or these components can be used separately in thetoner fusing process of the invention. Where nonfunctionalpolyorganosiloxane is included, it can serve as a diluent for polymer ofthe invention and for functional polyorganosiloxane (if included), so asto lessen the release agent expense.

With reference to the blends and mixtures, the presence of thepolyorganosiloxane component, as part of the polymer of the invention,promotes dispersal of the polymer in the one or more nonfunctionaland/or functional polyorganosiloxanes, and stabilizes the polymer,thereby combating (e.g., preventing or at least inhibiting)settling—particularly where the polymer of the invention serves as anadditive. Without this polyorganosiloxane component, hydrocarbons,particularly waxy hydrocarbons, that are added to or combined withsilicone or polyorganosiloxane liquids and oils, will tend to phaseseparate or precipitate. This will occur at ambient temperatures and atelevated temperatures; however, the tendency is particularly evidentwith cooling compositions.

In the release agent blends and mixtures, preferably the blockpolyorganosiloxane block organomer polymer of the invention ispredominantly polyorganosiloxane—i.e., as a matter of preference, thepolyorganosiloxane component of the polymer is predominant. Because ofthis predominance, the polymer of the invention more easily disperses inthe one or more nonfunctional and/or functional polyorganosiloxanes, andthusly disperses more easily therein as an additive.

Where a release agent blend or mixture includes a nonfunctionalpolyorganosiloxane, and where the polymer of the invention comprises notmore than 50 percent by volume of the blend or mixture, then preferablythe polyorganosiloxane component, of the block polyorganosiloxane blockhydrocarbon polymer, has a similar, or even identical—or at leastsubstantially or essentially identical—chemical structure to that of thenonfunctional polyorganosiloxane. As a matter of particular preferencein this instance, both the nonfunctional polyorganosiloxane of the blendor mixture, and the polyorganosiloxane component—i.e., the one or morepolyorganosiloxane blocks—of the block polyorganosiloxane blockorganomer polymer, are nonfunctional polydimethylsiloxanes.

However, if the release agent blend or mixture comprises more than 50percent by volume, of the polymer of the invention, then it is notsignificant whether the indicated chemical structures are the same ordifferent. In this instance, the block polyorganosiloxane blockorganomer polymer of the invention may be considered the primarycomponent of the blend or mixture, and not an additive.

Release agent blends and mixtures of the invention preferably have aviscosity of from about 150 to about 100,000 cSt, at 25° C. Morepreferably, these blends and mixtures have a viscosity of from about 200to about 70,000 cSt, at 25° C.

Suitable release agent compositions of the invention include thosecomprising about 30 percent or less by weight of the blockpolyorganosiloxane block organomer polymer of the invention. Thecompositions further can include polyorganosiloxanes, as discussed,particularly nonfunctional polyorganosiloxanes.

A preferred release agent composition of the invention comprises about4.4 percent by weight block polyorganosiloxane block organomer polymerof the invention, in a 60,000 cSt polydimethylsiloxane liquid. Anotherpreferred release agent composition of the invention comprises about12.5 percent by weight of the polymer in a 350 cSt polydimethylsiloxaneliquid. Preferably in these compositions, the polymer of the inventionis dispersed in the polydimethylsiloxane liquid.

And where the organomer component comprises one or more halocarbylblocks and/or one or more perhalopolyether blocks, the polymer of theinvention will be effective even at very low levels. Here the polymermay comprise as little as about 1 percent by weight, or even 0.5 percentby weight, of the release agent composition.

Further in this regard, suitable release agent compositions of theinvention include those comprising from about 0.5 percent to about 50percent by weight block polyorganosiloxane block organomer polymer ofthe invention, in a nonfunctional polyorganosiloxane having a viscosityof from about 100 cSt to about 160,000 cSt. More preferred arecompositions comprising from about 2 percent to about 20 percent byweight block polyorganosiloxane block organomer polymer of theinvention, in a nonfunctional polyorganosiloxane having a viscosity offrom about 200 cSt to about 100,000 cSt. Still more preferred arecompositions comprising from about 4 percent to about 15 percent byweight block polyorganosiloxane block organomer polymer of theinvention, in a nonfunctional polyorganosiloxane having a viscosity offrom about 250 cSt to about 80,000 cSt.

Also suitable are release agent compositions comprising from about 1percent to about 15 percent by weight block polyorganosiloxane blockorganomer polymer of the invention, and from about 1 percent to about 15percent by weight functional polyorganosiloxane, in a nonfunctionalpolyorganosiloxane having a viscosity of from about 100 cSt to about160,000 cSt—more preferably, of from about 200 cSt to about 80,000 cSt.Suitable functional polyorganosiloxanes for this purpose are thecarboxy, amino, mercapto, silane, and phenol functionalpolyorganosiloxanes.

With respect to the foregoing, the preferred nonfunctional andfunctional polyorganosiloxanes are the nonfunctional and functionalpolydimethylsiloxanes.

A particular release agent composition of the invention comprises about4.4 percent by weight polymer of the invention in 60,000 cSt DC200®polydimethylsiloxane, with the polymer prepared from Unicid® 700 and anα-aminopropyldimethylsiloxy, ω-trimethylsiloxy terminatedpolydimethylsiloxane having a molecular weight of about 12,000. As avariation, 250 cSt DC200® polydimethylsiloxane may be used, with thecomposition comprising 12.5 weight percent by weight of the polymer.

In another variation of the indicated 4.4 percent composition, theorganomer component of the polymer is derived from perfluorododecanoicacid. And a variation of this composition comprises about 0.5 percent byweight of the indicated fluorine-containing polymer; yet anothervariation also comprises 0.5 percent of this fluorinated polymer, but in250 cSt DC200® polydimethylsiloxane.

Yet another release agent composition of the invention comprises bothabout 4.4 percent by weight of the indicated Unicid®700/aminofunctionalPDMS polymer, and also about 0.5 percent by weight of the indicatedperfluorododecanoic acid/aminofunctional PDMS polymer, in 60,000 cStDC200® polydimethylsiloxane. A variation of this composition insteadutilizes 250 cSt DC200® polydimethylsiloxane, and 12.5 percent by weightof the Unicid®700/aminofunctional polydimethylsiloxane polymer.

Yet another release agent composition of the invention comprises about2.2 percent by weight polymer of the invention, about 2.2 percent byweight α,ω carboxypropyldimethylsiloxy terminated polydimethylsiloxanehaving a molecular weight of about 24,000, and about 0.22 percent byweight stearic acid, in 60,000 cSt DC200 polydimethylsiloxane. Thepolymer of the invention is prepared from stearic acid and anα-aminopropyldimethylsiloxy, ω-trimethylsiloxy terminatedpolydimethylsiloxane having a molecular weight of about 12,000.

The release agent of the invention can be employed in the same manner asrelease agents conventionally are used in toner fusing systems.Specifically, the release agent is applied to the surface of a fusermember, so that during the fusing process the release agent contactstoner on the substrate, and can contact the substrate. The release agentis accordingly transferred to the toner surface through contact with thefuser member surface. Preferably the release agent is applied so as toform a film that completely, or at least essentially, or at leastsubstantially, covers the fuser member surface. Also as a matter ofpreference, during the operation of the toner fusing system the releaseagent is applied continuously, or at least essentially continuously, orat least substantially continuously, to the surface of the fuser member.

Further as to application, where the release agent comprises more thanone ingredient or component (e.g., two or more block polyorganosiloxaneblock organomer polymers of the invention; or one or more polymers ofthe invention, along with one or more nonfunctional polyorganosiloxanes,and/or one or more functional polyorganosiloxanes), the components maybe applied simultaneously to the fuser as a blend, or in separateapplications using the same or multiple applicators. In the case ofmultiple applicators, the blend is produced on the fuser member surface.

Typical rates for application to substrate, in the case of paper, areless than 30 microliters (μl) per 8½″ by 11″ sheet. Application ratesare limited by unwanted side effects, such as oil streaks, machinecontamination during duplex printing, and oil spots.

Application to the fuser member may be by any suitable applicator,including release agent soaked web, pad, or impregnated roll.Preferably, a means that provides the indicated continuous application,such as a rotating wick oiler or a donor roller oiler, is employed.

A rotating wick oiler comprises a storage compartment for the releaseagent, or component thereof, and a wick for extending into thiscompartment. During operation of the toner fusing system of theinvention, the wick is situated so as to be in contact with the storedrelease agent, or component thereof, and also with the fusing surfacelayer of the fuser member; the wick thusly picks up release agent, orcomponent thereof, and transfers it to the fuser member.

A donor roller oiler is an applicator which includes a metering rollerthat takes up release agent, or component thereof, from its supplysource, a metering blade, which can be a rubber, plastic, or metalblade, that skims excess from the metering roller, and a delivery rollerthat receives release agent or component thereof from the meteringroller, and contacts the fuser member surface to apply release agent orcomponent thereon.

The fuser and support members may be of the type as are generallyemployed in toner fusing processes. Internal and/or external heating maybe employed, and heating means as are known in the art are suitable.Preferably, the means of providing heat for fusing toner and substratecomprise the heating of the fuser member by one or more external and/orinternal heating sources, and transmission of this heat from the fusermember to the toner, or to both toner and substrate—preferably bycontact.

The fuser member surface may be comprised of any suitable material ormaterials—preferably, a material or materials such as are conventionalin the art. Among the materials that may be used are the polysiloxaneelastomers, or silicone rubbers or elastomers; two appropriatecommercially available silicone rubbers are Silastic™-J, from DowCorning Corporation, and EC4952, from Emerson & Cuming ICI, Billerica,Mass. Further eligible materials are polyfluorocarbons, including thefluoroelastomers. Commercially available fluoroelastomers that may beused are those sold by Dupont Dow Elastomers, Stow, Ohio under thetrademark Viton®, such as Viton® A, Viton® GF, etc. Also eligible arenonelastomeric fluorocarbon materials, such as fluoroplastics andfluororesins, like polytetrafluoroethylene (PTFE), and copolymers oftetrafluoroethylene (TFE) and perfluoroalkylvinylether (PFA), andfluorinated ethylene propylene copolymers; particularly, the fusermember may comprise a Teflon coating, or a PFA sleeve.

In an embodiment of the toner fusing process of the invention, theprecursors may be applied separately to the fuser member surface, withthe reaction that takes place between the precursors—to form the blockpolyorganosiloxane block organomer polymer of the invention—occurring onthe fuser member, and the heat of the fusing process facilitating thebonding. The point at which precursors combine can be controlled bywhere on the fusing surface the different precursors are applied. And bycontrolling the point of combination, the point of reactioncorrespondingly can be controlled.

The separate application is provided by employing a separate applicatorfor each precursor. Controlling the place of precursor application tothe fuser member—and thereby exerting the indicated control over pointof combination and of reaction—can be effected by the positioning ofapplicators for different precursors.

The advantage provided by absence, or at least essential absence, ofprimary amine and isocyanate, as discussed, also accrues where theprecursors are separately applied. Specifically, it is preferred thatall, or at least essentially all, of the primary amine and isocyanategroups be reacted on the fuser member, and it is accordingly preferredthat no, or at least essentially no, unreacted primary amine andisocyanate groups leave the fuser member, or otherwise reach or touchthe substrate or toner thereon.

The indicated control over combination and reaction can be utilized toprovide these desired results. Particularly, precursor application canbe conducted to promote the desired reaction on the fuser membersurface.

So when it is primary amino and carboxy or acid chloride functionalprecursors which are being employed, preferably the applicators arepositioned so that the primary amino functional precursor is appliedfirst and the carboxy or acid chloride functional precursor is appliedsubsequently, or at a position subsequent to the position forapplication of the primary amino functional precursor, with aminofunctional precursor accordingly already being on the fuser membersurface; additionally as a matter of preference, the indicated carboxyor acid chloride excess is employed in this separate addition.Correspondingly, with isocyanate and hydroxy functional precursors, theapplicators preferably are positioned so that the isocyanate functionalprecursor is applied first and the hydroxy functional precursor isapplied subsequently, with isocyanate functional precursor accordinglyalready being on the fuser member surface; and here, preferably theindicated hydroxy excess is employed.

In the case of isocyanate and primary amine precursors, preferably therelative isocyanate and primary amine proportions as discussed areemployed. Also preferably, it is the isocyanate functional precursorthat is applied first.

Any suitable applicators may be used, as may any configuration ofmultiple applicators which will provide the requisite separateapplication. For instance, dual applicator systems that are known in theart, such as that disclosed in U.S. Pat. No. 4,034,706, may be employed;this patent is incorporated herein in its entirety, by referencethereto.

The invention is illustrated by the following procedures; these areprovided for the purpose of representation, and are not to be construedas limiting the scope of the invention. Unless stated otherwise, allpercentages, parts, etc. are by weight.

EXPERIMENTAL PROCEDURES Materials Employed in the Procedures

Unicid®350, 425, 550, and 700 (487, 595, 772, and 888 grams per molecarboxylic acid, respectively), from Baker Petrolite

α,ω-aminopropyldimethylsiloxy terminated polydimethylsiloxanes, all fromUnited Chemical Technologies, Inc.: PS510a and b (1370 and 2260 gramsper mole amine, respectively); PS511 (3086 grams per mole amine); andPS513a, b, c, and d (11660, 9300, 6165, and 7575 grams per mole amine,respectively)

PS563 α,ω-carboxypropyldimethylsiloxy terminated polydimethylsiloxane,31,200 grams per mole carboxylic acid, from United ChemicalTechnologies, Inc.

Stearic acid 98+%; perfluorodecanoic acid 95%; perfluorotetradecanoicacid 97%; perfluorosebacic acid; pentadecafluoroocatanoic acid 96%;dodecyl isocyanate; octylamine 99%; and monohydroxy polydimethysiloxane,about 4670 grams per mole hydroxyl: from Aldrich® Chemical, Milwaukee,Wis.

350, 1,000, and 60,000 centistoke DC200® polydimethylsiloxane, from DowCorning Corporation

Fomblin® MF-300 monocarboxy functional perfluoropolyether, 650 grams permole carboxylic acid, from Ausimont USA, Inc.

Monoamino polydimethylsiloxane additive: α-amino-propyldimethylsiloxy,ω-trimethylsiloxy terminated polydimethylsiloxane, number averagemolecular weight of 12,000, amine equivalent of about 13,000 grams permole amine

Monothiol polydimethylsiloxane additive: α-thiol-propyldimethylsiloxy,ω-trimethylsiloxy terminated polydimethylsiloxane, viscosity of about 80cSt, about 3,800 grams per mole thiol

PFA film, 80 microns thickness, from Saint-Gobain Performance Plastics,Wayne, N.J.

COMPARATIVE EXAMPLES 1-4

Table 1 below lists the ingredients, and amounts thereof, used toprepare the release fluids of Comparative Examples 1-4. As shown inTable 1, the Comparative Example 1 release fluid did not include anadditive. Each of the other release compositions comprised 4.4 percentby weight additive in polydimethylsiloxane; this diluent was the 60,000centistoke DC200®. The listed thiol, amine, and acid, were,respectively, the monothiol and monoamino polydimethylsiloxaneadditives, and the PS563.

TABLE 1 Comparative PDMS viscosity Additive 60K PDMS Example (cSt)*Additive amt (grams) (grams) 1 60,000 None None 800 2 60,000 Thiol 36764 3 60,000 Acid 36 764 4 60,000 Amine 36 764 *Measured using aBrookfield Viscometer, from Brookfield Engineering Laboratories,Stoughton, Ma

Preparation of Amide Polar Functionality Polymers and Release Fluids ofthe Invention

Amide functional block polyorganosiloxane block hydrocarbon polymers ofthe invention were prepared, and combined with diluent to providerelease compositions of the invention, as set forth in Examples 1-6.Specifically as to Example 6, in fact as stated therein, the attemptedpreparation of the polymer did not produce the desired result.

EXAMPLE 1

5.67 grams of Unicid®700 were combined with 94.33 grams of PS513a, andblended at 175° C. for 3 hours. 35.2 grams of the resulting product werecombined with 764.8 grams of 60,000 cSt DC200® oil, and blended at roomtemperature.

EXAMPLE 2

0.81 grams of stearic acid were combined with 40 grams of PS513b at80-85° C., until the resulting melt was completely blended, about 30minutes total. No precipitation of stearic acid was observed on cooling.20 grams of the resulting product were oven baked at 175° C. for 7 hoursto prepare the polymer. 17.6 grams of this product were combined with382.4 grams of 60,000 cSt DC200® oil, and blended at room temperature.

EXAMPLE 3

1.17 grams of stearic acid were combined with 40 grams of PS513b at80-85° C., until the resulting melt was completely blended. No grossprecipitation of the stearic acid was observed on cooling; a slight hazewas noted. 20 grams of the resulting product were oven baked at 175° C.for 7 hours to prepare the polymer. 17.6 grams of this product werecombined with 382.4 grams of 60,000 cSt DC200® oil, and blended at roomtemperature.

EXAMPLE 4

2.518 grams of Unicid®700 and 40 grams of PS513b were combined in aflask and heated to about 110° C., with stirring, until melt blended. 20grams of the resulting product were oven baked at 175° C. for 7 hours toprepare the polymer. 17.6 grams of this product were combined with 382.4grams of 60,000 cSt DC200® oil, and blended at room temperature.

EXAMPLE 5

3.6? grams of Unicid®700 and 40 grams of PS513b were combined in a flaskand heated to about 110° C., with stirring, until melt blended. 20 gramsof the resulting product were oven baked at 175° C. for 7 hours toprepare the polymer. 17.6 grams of this product was combined with 382.4grams of 60,000 cSt DC200® oil, and blended at room temperature.

EXAMPLE 6

13.33 grams of Unicid®700 and 20 grams of PS510a were combined in aflask and heated to about 115° C., with stirring, until melt blended. 20grams of the resulting product, which was a waxy solid, were oven heatedat 150° C. for 6 hours, producing a dark brown blend that formed apartial gel as well as phase separating. The heat stability of the blendwas not very good, as evidenced by the gel formation and color.

Testing Release Compositions for Combating Toner Offset

An Imagesource 110 electrostatographic copier, from Heidelberg DigitalL.L.C., Rochester, was used to test the release compositions ofparticular Examples and Comparative Examples, to determine theireffectiveness in combating toner contamination. Contamination wasmeasured from the toner offset to the cleaning web of the copier.

For the tests, the compositions of the Examples and Comparative Exampleswere used in place of the standard release oil, and the copierreproduction rate was accelerated to 150 prints per minute.Additionally, a polyester toner was employed, and the fuser setpointtemperatures were varied between a high (365° F.) temperature setpointand a low (335° F.) temperature setpoint. Otherwise, the materials,hardware, and operating parameters of the copier were left unchanged.

In its operation, the Imagesource 110 copier employs two heater rollersto heat the fuser roller. Toner offset from paper in the copying processis removed from the fuser roller by the heater rollers, by virtue of thehigh surface energy of the anodized aluminum surface of the heaterrollers. The indicated cleaning web is a thin Nomex® web, used to removetoner offset from the heater rollers by contact with both.

With all of the release agent compositions, test runs of 2500 printswere made using a multiple density image. Contamination of the cleaningweb was determined by measuring and averaging the optical transmissiondensity, of toner collected on the cleaning web surface. Opticaltransmission density was measured using an X-Rite 310 TransmissionDensitometer, from X-Rite Company, Grand Rapids, Mich.

The density of the toner offset collected by the cleaning web estimatesthe offset rate of the fuser. As discussed, this offset acts ascontamination, and accordingly offset rate indicates the degree ofcontamination. Therefore, the density of this offset on the web is ameasure of the degree of contamination.

In making measurements here, clean webs were used to set the measuredoptical transmission density to zero. As to the results, in general withrespect to contamination, cleaning web transmission densities below 0.3are excellent, at 0.31 to 0.5 are good, at 0.51 to 0.79 are marginal,and at 0.8 and above are unacceptable.

However, with certain toners—e.g., polyester toners, such as thoseemployed here—even lower contamination levels are desirable, in order toavoid irreversible buildup of contamination on the heater rollers.Specifically, it is believed that in these instances, achievingdensities below 0.2 is the objective.

In any event, with respect to density values, a higher web transmissiondensity indicates an increased fuser offset rate, and thusly a greaterdegree of contamination. Contamination leads to offset onelectrostatographic apparatus parts and on images, and yet additionallyreduces roller life.

The web transmission density values obtained from the contaminationtests are set forth in Table 2.

TABLE 2 High temp Low temp Average Comparative Example 1 1.35 0.61 0.98Comparative Example 2 0.31 1.5 0.905 Comparative Example 3 0.37 0.610.49 Comparative Example 4 0.15 0.23 0.19 Example 1 0.21 0.06 0.135Example 3 0.14 0.36 0.25 Example 4 0.15 0.18 0.165

The data shown in Table 2 demonstrate that the results obtained, withthe amide functional polymers of the invention, were superior to thoseprovided by the nonfunctional, thiol functional, and acid functionalsilicones. The Table 2 values further demonstrate that on average, thepolymers of the invention prepared from Unicid 700 block performedbetter than the amine functional oil.

Further as to offset, it is noted that toner not collected by thecleaning web may remain on the heater rollers. In this regard, after thetests the heater rollers were checked for contamination. The results areshown in Table 3.

TABLE 3 High temp Low temp Comparative Example 1 None Y ComparativeExample 2 None Y Comparative Example 3 None Y Comparative Example 4 NoneNone Example 1 None None Example 3 None Y Example 4 None None

As can be seen, release compositions of the invention resistedcontamination where the hydrocarbyl block was longer than 18 carbons;however, with the stearyl block, the heater rollers were not protected.The nonfunctional, thiol functional, and acid functional oils alsocontaminated the heater rollers.

EXAMPLE 7

68.39 grams of the monoamino polydimethylsiloxane additive and 1.61grams of stearic acid were combined and stirred at 105° C. for 15minutes. A 5 gram sample was removed, and the temperature of theremainder was elevated to 150° C. After 15 additional minutes another 5gram sample was removed, and stirring of the remainder was continued at150° C. Thereafter, every 30 minutes yet another 5 gram sample wasremoved until a total of 180 minutes of heating was completed.

The samples were measured for residual amine content by potentiometrictitration in a tetrahydrofuran/methanol mixture. The results are shownin Table 4.

TABLE 4 Temperature Total Time Percent amine (° C.) (minutes) remaining105 15 89 150 30 32 150 60 21 150 90 13 150 120 7 150 150 4 150 180 1

The values set forth in Table 4 indicate the rate of conversion of theamine. These data demonstrate that the reaction of the amine issubstantially complete within 3 hours at 150° C.

EXAMPLE 8

28.43 grams of PS513c and 1.57 grams of stearic acid were added to abeaker surrounded by a jacket heater, and having a Teflon stirbar forblending the beaker contents. A thermocouple was immersed in the mixtureof functional polydimethylsiloxane and stearic acid, in order to monitortemperature.

The mixture was heated to 120-130° C. and blended for 15 minutes.Thereafter the beaker was plunged partially into a water bath to rapidlycool the product. The product then was placed in an oven at 150° C. for6 hours, and stirred once after melting.

The cooled product, a light yellow semisolid, was added to the amount of350 cSt DC200® oil required to provide a composition comprising 12.5percent by weight of the product. The blend remained suspended after 72hours.

EXAMPLE 9

Example 8 was repeated, except instead with 1.32 grams of stearic acid,and a mixing time of 1 minute. The cooled product was a translucentyellow viscous liquid, which was added to the amount of 350 cSt DC200®oil required to provide a composition comprising 12.5 percent by weightof the product. The blend remained suspended after 72 hours.

EXAMPLE 10

Example 8 was repeated again, except here with 1.11 grams of stearicacid, and a mixing time of 5 minutes. The cooled product was atranslucent light yellow viscous liquid, which was added to 350 cStDC200® oil to form a 12.5 percent by weight composition. The blendremained suspended after 72 hours.

EXAMPLE 11

27.8 grams of PS513c and 2.20 grams of Unicid®350-were combined andblended as described in Example 8, except at 120° C., and for 5 minutes.After oven baking, the cooled product was a light tan opaque semisolid.The product was added to 350 cSt DC200® oil to form a 12.5 percent byweight composition. The blend remained suspended after 72 hours.

EXAMPLE 12

27.36 grams of PS513c and 2.64 grams of Unicid® 425 were combined andblended as described in Example 11. After oven baking, the cooledproduct was a light tan opaque semisolid. The product was added to 350cSt DC200® oil to form a 12.5 percent by weight composition. The blendremained suspended after 72 hours.

EXAMPLE 13

26.66 grams of PS513c and 3.34 grams of Unicide 550 were combined andblended as described in Example 11. After oven baking, the cooledproduct was a light tan opaque semisolid. The product was added to 350cSt DC200® oil to form a 12.5 percent by weight composition. The blendremained suspended after 72 hours.

EXAMPLE 14

27.47 grams of PS511b and 2.53 grams of stearic acid were combined andblended at 105° C. for 5 minutes, then placed in an oven at 150° C. for6 hours. The resulting product, a deep yellow translucent soft solid,was added to 350 cSt DC200® oil to form a 12.5 percent by weightcomposition.

EXAMPLE 15

5 grams of PS510a and 1 gram of stearic acid were combined and heated at150° C. for 20 minutes, and the product was subjected to Fouriertransform infrared spectroscopy (IR). Infrared spectroscopy of thefunctional groups was used to determine the state of the reaction.

The spectroscopy showed formation of an amide peak at 3312. However, thespectra of the relevant compounds—i.e., the acid and amine reactants,and the prospective amide product—were difficult to observe, due to thehigh molecular weight of the PS510a, and the resulting low concentrationof the compounds' functional groups. Therefore, in place of PS510a,octadecylamine—with a much lower molecular weight, and therefore ahigher amine concentration—was employed as a model amine and reactedwith the stearic acid, so that the changes in infrared adsorption couldbe ascertained.

0.425 grams of Octadecylamine and 0.468 grams of stearic acid (1:1 moleratio of carboxylic acid to primary amine groups) were combined andheated at 150° C. for 1 hour. IR showed an amide peak at 3310,elimination of the primary amine peak at 3330, and substantial reductionof the stearic acid peak at about 1700. These results indicate that thereaction of amine and acid, to produce amide, did occur.

Preparation of Fluorocarbon Block Polymers and Release Fluids of theInvention EXAMPLE 16

0.0558 grams of MF-300 and 1 gram of PS513a (1:1 molar ratio ofcarboxylic acid to primary amine groups) were combined at roomtemperature. The silicone and perfluoropolyether blended easily to asingle clear phase.

This mixture was heated in an oven at 175° C. for 1 hour, and formed ahazy pale yellow liquid. This product was added to 1,000 cSt DC200® oilto form a 12.5 percent by weight composition.

EXAMPLE 17

2 grams of perfluorododecanoic acid and 37.9 grams of PS513a werecombined in a beaker and placed on a hot plate with a Teflon stir bar.The mixture was stirred at 100° C. for about 3 hours, and formed a hazyyellow liquid. This product was added to 1,000 cSt DC200® oil to form a12.5 percent by weight composition.

EXAMPLE 18

5.67 grams of Unicid®700 were combined with 94.33 grams of PS513a, andblended at 175° C. for 3 hours. 35.2 grams of the resulting product wereadded to 1,000 cSt DC200® oil to form a 12.5 percent by weightcomposition.

COMPARATIVE EXAMPLES 5-8

Comparative Examples 5-8 were prepared in substantially the same manneras Comparative Examples 1-4, respectively, except with 1,000 cSt DC200®,and 12.5 percent additive.

Wetting of PTFE

Drops of the oils of Examples 16-18 and Comparative Examples 5-8 wereplaced on a cleaned Teflon sheet. A VCA-2500 XE video contact anglemeasurement apparatus, from ASE Americas, Inc., Billerica, Mass., wasused to measure the contact angle of the drops with the Teflon surface.The time elapsed between the placement of the drop and when the drop wasmeasured is indicated. After the first set of measurements, a portion offluid from the top of the drop was removed with a syringe to determinethe receding contact angle. The drop was then heated to 200° C. for 10minutes and remeasured.

The contact angle measurements thusly obtained are shown in Table 5.

TABLE 5 Advancing angle at room temperature After (all at 12.5% Time:200° C. for additive) 0 min 10 min 30 min Receding 10 MinutesComparative 31, 40 32, 36 31, 34 14, 9 24, 26 Example 5 Comparative 34,35 33, 40 28, 29 11, 9 — Example 6 Comparative 38, 36 33, 35 38, 37 27,28 — Example 7 Comparative 36, 38 30, 34 24, 26 24, 33 25, 23 Example 8Example 16 34, 35 22, 28 22, 24 7, 8 0* Example 17 32, 33 21, 26 16, 180* 0* Example 18 42, 38 34, 38 36, 34 18, 15 — — not tested *angle toosmall to measure, less than 2 degrees or zero.

The values set forth in Table 5 demonstrate the improved wetting offluorocarbon surfaces with block polyorganosiloxane block fluorocarbonrelease compositions of the invention. Most fluids show no tendency towet Teflon; this is not the case with the fluorocarbon blockcompositions of Examples 16 and 17. Receding angles were lower andnoisy. While the fluorocarbon block compositions show zero or very lowangles, the nonfunctional oil of Comparative Example 5 appears lowerthan the functional oils. However, once heated, the nonfunctionalpolydimethylsiloxane quickly regained a high contact angle, while thefluorocarbon block oils fully wet the Teflon surface. The hydrocarbonblock oil of Example 18 showed no greater tendency than the oils ofComparative Examples 5-8 to wet Teflon surfaces.

EXAMPLE 19

0.431 grams of perfluorotetradecanoic acid and 4.581 grams of PS513dwere combined in a beaker, and heated to about 120-130° C., with mixing.The resulting mixture evolved some gas bubbles and became a viscousliquid with a clear yellow cast. On cooling, the mixture remainedtranslucent after more than 1 week. This product was then heated in anoven at 150° C. for 6 hours, with occasional stirring, and thereafterallowed to cool. On cooling, the product was a transparent semisolidwith a slight haze.

EXAMPLE 20

0.4 grams of perfluorosebacic acid and 3.11 grams of PS513d werecombined in a beaker, and heated to about 140-150° C., with mixing. Theresulting mixture evolved some gas bubbles and became a viscous liquidwith a translucent yellow cast. On cooling, the mixture turned opaqueafter about 2 days. This product was then heated in an oven at 150° C.for 6 hours, with occasional stirring, and thereafter allowed to cool.On cooling, the product was a clear darker yellow semisolid.

EXAMPLE 21

0.254 grams of pentadecafluoroocatanoic acid and 4.625 grams of PS513dwere combined in a beaker, and heated to about 100° C., with mixing. Theresulting mixture evolved some gas bubbles and became a clear liquidwith a yellow cast. On cooling, the mixture became opaque after about 2days. This product was then heated in an oven at 150° C. for 6 hours,with occasional stirring. On cooling, the product was a translucentsemisolid.

EXAMPLE 22

0.295 grams of perfluorododecanoic acid and 3.64 grams of PS513d werecombined in a beaker, and heated to about 110-120° C., with mixing. Theresulting mixture evolved some gas bubbles and attained a clear yellowcast. On cooling, the mixture remained translucent after more than 48hours. This product was then heated in an oven at 150° C. for 6 hours,with occasional stirring. On cooling, the product was a lightyellow-brown translucent semisolid.

EXAMPLE 23

0.278 grams of perfluorotetradecanoic acid and 5.146 grams of themonoamino polydimethylsiloxane additive were combined in a beaker, andheated to about 110-120° C., with mixing. The mixture evolved some gasbubbles and attained a clear yellow cast. On cooling, the mixtureremained clear after more than 2 days. This product was then heated inan oven at 150° C. for 6 hours, with occasional stirring. On cooling,the product was a deep yellow clear fluid.

EXAMPLE 24

0.354 grams of perfluorosebacic acid and 4.787 grams of the monoaminopolydimethylsiloxane additive were combined in a beaker, and heated toabout 140-150° C., with mixing. The mixture evolved some gas bubbles andbecame a viscous liquid with a translucent yellow cast. On cooling, themixture turned opaque after about 2 days. This product was then heatedin an oven at 150° C. for 6 hours, with occasional stirring. On cooling,the product was a clear yellow semi-solid with a slight haze.

EXAMPLE 25

0.172 grams of pentadecafluoroocatanoic acid and 5.553 grams of themonoamino polydimethylsiloxane additive were combined in a beaker, andheated to about 100° C., with mixing. The mixture evolved some gasbubbles and became a clear liquid with a yellow cast. On cooling, themixture remained clear after more than 2 days. This product was thenheated in an oven at 150° C. for 6 hours, with occasional stirring. Oncooling, the product was a clear yellow fluid.

EXAMPLE 26

0.263 grams of perfluorododecanoic acid and 5.716 grams of the monoaminopolydimethylsiloxane additive were combined in a beaker, and heated toabout 110-120° C., with mixing. The mixture evolved some gas bubbles andattained a clear yellow cast. On cooling, the mixture remained clearafter more than 48 hours. This product was then placed in an oven at a150° C. for 6 hours, with occasional stirring. On cooling, the productwas a clear yellow fluid.

Wetting of a PFA Surface

A 1 inch by ½ inch rectangle of the PFA sleeve material was cleaned with200 proof ethanol and taped flat. Release fluids were prepared from thefluorocarbon block polymer additives of Examples 20 and 22-25, by addingtogether the amounts of additive and 350 cSt DC200® oil as set forth inTable 6, so as to provide compositions comprising 12.5 percent by weightof the additive. A control, of 350 cSt DC200® oil with no additive, wasalso employed.

With each composition, a drop of release fluid was placed on the surfaceand spread thinly and evenly with a small wooden stick. The dimensionsof the spread patch were noted and the sample monitored—in accordancewith the conditions set forth in Table 6—for dewetting from the PFAsurface.

The samples were subjected to observation and treatment, in accordancewith the conditions set forth in Table 6, to determine the extent ofdewetting. In this regard, dewetting is characterized by the spreadlayer pulling together into one or more small droplets, while partialdewetting is characterized by a slight contraction of the spread film.

The results observed also are shown in Table 6.

TABLE 6 DC200 350 Additive cSt fluid After heating (amt in (amt in to150° C. grams) grams) Observation Time for 3 hours Control 3.0 Rapidlydewet 1 min Dewet (none) Example 20 2.625 Partially dewet 30-40 minDewet (0.375) Example 22 2.620 Remained spread >2 hour Partially (0.378)dewet Example 23 2.625 Slowly dewet 30-40 min Dewet (0.376) Example 242.630 Partially dewet 30-40 min Dewet (0.372) Example 25 2.626 Remainedspread >2 hour Remained (0.376) spread Example 25 2.92 Remainedspread >2 hour Dewet (0.0177) Example 25 3.155 Slowly dewet 20 min Dewet(0.00094)

Preparation of Urea and Urethane Polar Functionality Polymers of theInvention EXAMPLE 27

16.05 grams of the monoamino polydimethylsiloxane additive was placed ina flask. The flask was closed with a stopper, which was provided with anoutlet for escaping gas. A nitrogen source was inserted through thestopper, with its outlet placed below the surface of the liquidadditive. The liquid was stirred with a magnetic stir bar. For 18 hours,dry nitrogen from the source was bubbled through the outlet into thestirred liquid, thereby purging the liquid, forming a nitrogenatmosphere in the flask, and exiting through the outlet. After this 18hour purge, the nitrogen source outlet was raised above the surface ofthe liquid, with nitrogen output continuing, thereby maintaining thenitrogen atmosphere. 0.285 ml (0.25 grams) of dodecyl isocyanate wasinjected through the stopper into the flask. With stirring alsocontinuing, the siloxane and the isocyanate were blended at roomtemperature. The liquid turned clear and became more viscous, attaininga light straw color. The liquid remained clear after more than 72 hours.

EXAMPLE 28

Example 27 was repeated, except with 11.05 grams of monohydroxypolydimethylsiloxane in place of the monoamino polydimethylsiloxane, andwith 0.57 ml (0.5 grams) of dodecyl isocyanate. The liquid generatedbubbles, turned hazy, and became more viscous.

Finally, although the invention has been described with reference toparticular means, materials, and embodiments, it should be noted thatthe invention is not limited to the particulars disclosed, and extendsto all equivalents within the scope of the claims.

1. A process for fusing toner residing on a substrate to the substrate,the process comprising: (I) applying, to the surface of a fuser memberduring the toner fusing process, a release agent composition comprisinga polymer, the polymer comprising: (a) a polyorganosiloxane component,the polyorganosiloxane component comprising at least onepolyorganosiloxane block; (b) an organomer component, the organomercomponent comprising at least one organomer block, the at least oneorganomer block comprising at least one member selected from the groupconsisting of perhalopolyether blocks, hydrocarbyl blocks comprising atleast about 40 C atoms, and halocarbyl blocks; and (c) at least onepolar linkage: (1) comprising a polar functionality having a polarityvalue of at least about 1.8; and (2) covalently bonding apolyorganosiloxane block of the polyorganosiloxane component, and anorganomer block of the organomer component; and (II) contacting thetoner with the fuser member surface bearing the release agentcomposition.
 2. The process of claim 1, wherein the covalently bondedorganomer block comprises a hydrocarbyl block comprising at least about50 C atoms.
 3. The process of claim 1, wherein the covalently bondedorganomer block comprises a perfluoropolyether block.
 4. The process ofclaim 1, wherein the covalently bonded organomer block comprises afluorocarbyl block.
 5. The process of claim 4, wherein the polarfunctionality comprises a hydrogen bondable H atom.
 6. The process ofclaim 5, wherein the polar functionality has a polarity value of atleast about 2.0, and further comprises a hydrogen bond donor and ahydrogen bond acceptor, the hydrogen bond donor comprising the hydrogenbondable H atom.
 7. The process of claim 1, wherein the polarfunctionality comprises a hydrogen bondable H atom.
 8. The process ofclaim 7, wherein the polar functionality has a polarity value of atleast about 2.0, and further comprises a hydrogen bond donor and ahydrogen bond acceptor, the hydrogen bond donor comprising the hydrogenbondable H atom.
 9. A process for fusing toner residing on a substrateto the substrate, the process comprising: (I) applying, to the surfaceof a fuser member during the toner fusing process, a release agentcomposition comprising a polymer, the polymer comprising: (a) apolyorganosiloxane component, the polyorganosiloxane componentcomprising at least one polyorganosiloxane block; (b) an organomercomponent, the organomer component comprising at least one organomerblock, the at least one organomer block comprising at least one memberselected from the group consisting of perhalopolyether blocks andhydrocarbyl blocks; and (C) at least one polar linkage: (1) comprising apolar functionality having a polarity value of at least about 2.0, andcomprising a hydrogen bond acceptor and a hydrogen bond donor, thehydrogen bond donor comprising a hydrogen bondable H atom; and (2)covalently bonding a polyorganosiloxane block of the polyorganosiloxanecomponent, and an organomer block of the organomer component; and (II)contacting the toner with the fuser member surface bearing the releaseagent composition.
 10. The process of claim 9, wherein an atom of thehydrogen bond donor is covalently bonded to an atom of the hydrogen bondacceptor.
 11. The process of claim 9, wherein the hydtogen bond donorcomprises —NH—, and the hydrogen bond acceptor comprises —CO—.
 12. Theprocess of claim 9, wherein the polar functionality comprises an amideincorporating group.
 13. The process of claim 12, wherein the amideincorporating group comprises an amide group.
 14. The process of claim12, wherein the amide incorporating group comprises a member selectedfrom the group consisting of a urea group and a urethane group.
 15. Theprocess of claim 9, wherein the molecular weight of thepolyorganosiloxane component comprises more than 50 percent of themolecular weight of the polymer.
 16. The process of claim 9, wherein atleast one polar linkage comprises a C₃ or greater hydrocarbyl spacergroup connecting the polar functionality of the polar linkage to thepolyorganosiloxane block covalently bonded by the polar linkage, the C₃or greater hydrocarbyl spacer group comprising at least three carbonatoms separating the polar linkage from the polyorganosiloxane block.17. The process of claim 9, wherein: (a) the at least onepolyorganosiloxane block comprises a first polyorganosiloxane block anda second polyorganosiloxane block; (b) the at least one organomer blockcomprises a first organomer block; and (c) the at least one polarlinkage comprises: (1) a first polar linkage, covalently bonding thefirst polyorganosiloxane block and the first organomer block; and (2) asecond polar linkage, covalently bonding the second polyorganosiloxaneblock and the first organomer block.
 18. The process of claim 9,wherein: (a) the at least one polyorganosiloxane block comprises a firstpolyorganosiloxane block; (b) the at least one organomer block comprisesa first organomer block and a second organomer block; and (c) the atleast one polar linkage comprises: (1) a first polar linkage, covalentlybonding the first polyorganosiloxane block and the first organomerblock; and (2) a second polar linkage, covalently bonding the firstpolyorganosiloxane block and the second organomer block.
 19. The processof claim 9, wherein: (a) the at least one organomer block comprises atleast one hydrocarbyl block; and (b) for each polyorganosiloxane blockand each hydrocarbyl block, the mole ratio of polyorganosiloxane blockSi atoms to hydrocarbyl block C atoms is from about 1:1.5 to about 30:1.20. The process of claim 9, wherein: (a) the at least onepolyorganosiloxane block comprises at least one polydimethylsiloxaneblock, the at least one polydimethylsiloxane block comprising a firstpolydimethylsiloxane block; (b) the at least one organomer blockcomprises at least one alkyl block, the at least one alkyl blockcomprising a first alkyl block; and (c) the at least one polar linkagecomprises a first polar linkage, covalently bonding the firstpolydimethylsiloxane block and the first alkyl block.
 21. The process ofclaim 20, wherein each alkyl block comprises at least about 30 C atoms.22. The process of claim 20, wherein for each polydimethylsiloxane blockand each alkyl block, the mole ratio of polyalkylsiloxane block Si atomsto alkyl block C atoms is from about 2:1 to about 20:1.
 23. The processof claim 20, wherein for each polydimethylsiloxane block and each alkylblock, the ratio of polydimethylsiloxane block molecular weight to alkylblock molecular weight is from about 12:1 to about 55:1.
 24. The processof claim 9, wherein: (a) the at least one polyorganosiloxane blockcomprises at least one polydimethylsiloxane block, the at least onepolydimethylsiloxane block comprising a first polydimethylsiloxaneblock; (b) the at least one organomer block comprises at least oneperfluoroalkyl block, the at least one perfluoroalkyl block comprising afirst perfluoroalkyl block; and (c) the at least one polar linkagecomprises a first polar linkage, covalently bonding the firstpolydimethylsiloxane block and the first perfluoroalkyl block.
 25. Theprocess of claim 24, wherein each perfluoroalkyl block comprises fromabout 8 C atoms to about 20 C atoms.
 26. The process of claim 24,wherein for each polydimethylsiloxane block and each perfluoroalkylblock, the mole ratio of polydimethylsiloxane block Si atoms toperfluoroalkyl block C atoms is from about 4:1 to about 70:1.
 27. Theprocess of claim 9, wherein: (a) the at least one polyorganosiloxaneblock comprises at least one polydimethylsiloxane block, the at leastone polydimethylsiloxane block comprising a first polydimethylsiloxaneblock; (b) the at least one organomer block comprises at least oneperfluoropolyether block, the at least one perfluoropolyether blockcomprising a first perfluoropolyether block; and (c) the at least onepolar linkage comprises a first polar linkage, covalently bonding thefirst polydimethylsiloxane block and the first pert luoropolyetherblock.
 28. The process of claim 27, wherein each perfluoropolyetherblock has a molecular weight of from about 400 to about 8,000.
 29. Theprocess of claim 27, wherein for each polydimethylsiloxane block andeach perfluoropolyether block, the mole ratio of polydimethylsiloxaneblock Si atoms to perfluoropolyether block C atoms is from about 2:1 toabout 70:1.
 30. The process of claim 9, wherein the molecular weight ofthe polyorganosiloxane component of the polymer comprises at least 75percent of the molecular weight of the polymer; the release agentcomposition further comprising a polyorganosiloxane release agent. 31.The process of claim 30, wherein: (a) the at least onepolyorganosiloxane block of the polymer comprises at least onenonfunctional polydimethylsiloxane block; and (b) the polyorganosiloxanerelease agent comprises a nonfunctional polydimethylsiloxane; thepolymer comprising not more than about 50 percent by volume of therelease agent composition.
 32. The process of claim 31, wherein: (a) theat least one organomer block of the polymer comprises at least onemember selected from the group consisting of alkyl blocks,perfluoropolyether blocks, and fluoroalkyl blocks; (b) the polymercomprises from about 2 percent to about 15 percent by weight of therelease agent composition; and (c) the nonfunctionalpolydimethylsiloxane has a viscosity of from about 250 cSt to about80,000 cSt.
 33. The process of claim 31, wherein: (a) the at least oneorganomer block of the polymer comprises at least one member selectedfrom the group consisting of alkyl blocks, perfluoropolyether blocks,and fluoroalkyl blocks; (b) the polymer comprises from about 1 percentto about 15 percent by weight of the release agent composition; and (c)the nonfunctional polydimethylsiloxane has a viscosity of from about 200cSt to about 80,000 cSt; the release agent composition furthercomprising from about 1 percent to about 15 percent by weight functionalpolyorganosiloxane release agent, the functional polyorganosiloxanerelease agent comprising a functional polyorganosiloxane selected fromthe group consisting of carboxy, amino, mercapto, silane, and phenolfunctional polyorganosiloxanes.
 34. A process for preparing a polymercomprising at least one polyorganosiloxane block, at least one organomerblock comprising at least one member selected from the group consistingof perhalopolyether blocks and hydrocarbyl blocks, and at least onepolar linkage comprising a polar functionality having a polarity valueof at least about 2.0, the polar functionality comprising a hydrogenbond acceptor and a hydrogen bond donor, the hydrogen bond donorcomprising a hydrogen bondable H atom, the at least one polar linkagecovalently bonding a polyorganosiloxane block and an organomer blockselected from the group consisting of perhalopolyether blocks andhydrocarbyl blocks, and the process comprising reacting reactantscomprising: (a) a polyorganosiloxane precursor comprising a first polarlinkage forming moiety, the first polar linkage forming moietycomprising a first polar functionality forming group; and (b) anorganomer precursor comprising at least one member selected from thegroup consisting of perhalopolyether precursors and hydrocarbonprecursors, and further comprising a second polar linkage formingmoiety, the second polar linkage forming moiety comprising a secondpolar functionality forming group; wherein the first and second polarlinkage forming moieties react to form the at least one polar linkage;with the first and second polar functionality forming groups reacting toform the polar functionality.
 35. The process of claim 34, wherein theorganomer precursor comprises a hydrocarbon precursor, the hydrocarbonprecursor comprising at least about 30 C atoms.
 36. The process of claim34, wherein the organomer precursor comprises a fluorocarbon precursor.37. The process of claim 34, wherein the organomer precursor comprises aperfluoropolyether precursor.
 38. The process of claim 34, wherein thepolyorgano-siloxane precursor has the formulaX-(D³)_(e)-[(D⁴)_(f)-ran-(T)_(g];) and is endcapped by

wherein X-(D³)_(e) is a linear moiety; [(D⁴)_(f)-ran-(T)_(g)] is abranched moiety;

R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, and R¹¹ are the same or different, and areselected from the group consisting of C₁-C₁₀ hydrocarbyl groups; X is apolar linkage forming moiety; T is (R¹¹)_(h)SiO_((4-h)/2); e is 1 to300; f is 25 to 5000; g is 2 to 100; and h is 0 or
 1. 39. The process ofclaim 34, wherein: (a) the first polar functionality forming groupcomprises one of an amidization reactive carboxyl group and anamidization reactive primary amine group; and (b) the second polarfunctionality forming group comprises the other of the amidizationreactive carboxyl group and the amidization reactive primary aminegroup; whereby the polyorganosiloxane precursor comprises one of acarboxy functional precursor and a primary amino functional precursor,and the organomer precursor comprises the other of the carboxyfunctional precursor and the primary amino functional precursor; withthe polar functionality comprising an amide group.
 40. The process ofclaim 39, wherein: (a) the polyorganosiloxane precursor and theorganomer precursor are added together; (b) the polyorganosiloxaneprecursor and the organomer precursor are brought to a temperaturesufficient to place the polyorganosiloxane precursor and the organomerprecursor in a liquid state; (c) the polyorganosiloxane precursor andthe organomer precursor are blended to a form a mixture; and (d) themixture is heated at a reaction temperature sufficient for effectingreaction of the amidization reactive carboxyl group and the amidizationreactive primary amine group to form the polar functionality comprisingthe amide group; the ratio of amidization reactive carboxyl groups toamidization reactive primary amine groups being sufficiently greaterthan 1:1 so that, at the completion of the process, there areessentially no remaining amidization reactive primary amine groups. 41.The process of claim 39, wherein: (a) the polyorganosiloxane precursorcomprises a member selected from the group consisting ofpolydimethylsiloxane precursors having one first polar linkage formingmoiety and polydimethylsiloxane precursors having at least two firstpolar linkage forming moieties, each first polar functionality forminggroup comprising an amidization reactive primary amine group; wherebythe polyorganosiloxane precursor comprises a primary amino functionalprecursor; and (b) the organomer precursor comprises a member selectedfrom the group consisting of: (1) hydrocarbon precursors comprising atleast about 30 C atoms and having one second polar linkage formingmoiety, the second polar functionality forming group comprising anamidization reactive carboxyl group; (2) saturated monocarboxylic fattyacids having the formulaH₃C(CH₂)_(n)COOH wherein n is 4 to 28; and (3) saturated dicarboxylicfatty acids having the formulaHOOC(CH2)_(n)COOH wherein n is 4 to 28; whereby the organomer precursorcomprises a carboxy functional precursor.
 42. The process of claim 39,wherein: (a) the polyorganosiloxane precursor comprises a memberselected from the group consisting of polydimethylsiloxane precursorshaving one first polar linkage forming moiety and polydimethylsiloxaneprecursors having at least two first polar linkage forming moieties,each first polar functionality forming group comprising an amidizationreactive primary amine group; whereby the polyorganosiloxane precursorcomprises a primary amino functional precursor; and (b) the organomerprecursor comprises a member selected from the group consisting of: (1)saturated perfluoroalkanoic monocarboxylic acids having the formulaF₃C(CF₂)_(n)COOH wherein n is 4 to 28; and (2) saturatedperfluoroalkanoic dicarboxylic acids having the formulaHOOC(CF₂)_(n)COOH wherein n is 4 to 28; whereby the organomer precursorcomprises a carboxy functional precursor.
 43. The process of claim 39,wherein: (a) the polyorganosiloxane precursor comprises a memberselected from the group consisting of polydimethylsiloxane precursorshaving one first polar linkage forming moiety and polydimethylsiloxaneprecursors having at least two first polar linkage forming moieties,each first polar functionality forming group comprising an amidizationreactive primary amine group; whereby the polyorganosiloxane precursorcomprises a primary amino functional precursor; and (b) the organomerprecursor comprises a member selected from the group consisting ofperfluoropolyether precursors having one first polar linkage formingmoiety and perfluoropolyether precursors having at least two first polarlinkage forming moieties, each second polar functionality forming groupcomprising an amidization reactive carboxyl group; whereby the organomerprecursor comprises a carboxy functional precursor.
 44. The process ofclaim 34, wherein: (a) the first polar functionality forming groupcomprises one of an amidization reactive acid chloride group and anamidization reactive primary amine group; and (b) the second polarfunctionality forming group comprises the other of the amidizationreactive acid chloride group and the amidization reactive primary aminegroup; whereby the polyorganosiloxane precursor comprises one of an acidchloride functional precursor and a primary amino functional precursor,and the organomer precursor comprises the other of the acid chloridefunctional precursor and the primary amino functional precursor; withthe polar functionality comprising an amide group.
 45. The process ofclaim 44, wherein: (a) the polyorganosiloxane precursor and theorganomer precursor are added together; (b) the polyorganosiloxaneprecursor and the organomer precursor are brought to a temperaturesufficient to place the polyorganosiloxane precursor and the organomerprecursor in a liquid state; and (c) the polyorganosiloxane precursorand the organomer precursor are blended to a form a mixture; the ratioof amidization reactive acid chloride groups to amidization reactiveprimary amine groups being sufficiently greater than 1:1 so that, at thecompletion of the process, there are essentially no remainingamidization reactive primary amine groups.
 46. The process of claim 34,wherein: (a) the first polar functionality forming group comprises oneof an isocyanate group and a primary amine group; and (b) the secondpolar functionality forming group comprises the other of the isocyanategroup and the primary amine group; whereby the polyorganosiloxaneprecursor comprises one of an isocyanate functional precursor and aprimary amino functional precursor, and the organomer precursorcomprises the other of the isocyanate functional precursor and theprimary amino functional precursor; with the polar functionalitycomprising a urea group; wherein; the polyorganosiloxane precursor andthe organomer precursor are added together; the polyorganosiloxaneprecursor and the organomer precursor are brought to a temperaturesufficient to place the polyorganosiloxane precursor and the organomerprecursor in a liquid state; and the polyorganosiloxane precursor andthe organomer precursor are blended to a form a mixture; the ratio ofprimary amine groups to isocyanate groups being sufficiently greaterthan 1:1 so that, at the completion of the process, there areessentially no remaining isocyanate groups.
 47. The process of claim 34,wherein: (a) the first polar functionality forming group comprises oneof an isocyanate group and a hydroxyl group; and (b) the second polarfunctionality forming group comprises the other of the isocyanate groupand the hydroxyl group; whereby the polyorganosiloxane precursorcomprises one of an isocyanate functional precursor and a hydroxyfunctional precursor, and the organomer precursor comprises the other ofthe isocyanate functional precursor and the hydroxy functionalprecursor; with the polar functionality comprising a urethane group;wherein: the polyorganosiloxane precursor and the organomer precursorare added together; the polyorganosiloxane precursor and the organomerprecursor are brought to a temperature sufficient to place thepolyorganosiloxane precursor and the organomer precursor in a liquidstate; and the polyorganosiloxane precursor and the organomer precursorare blended to a form a mixture; the ratio of hydroxyl groups toisocyanate groups being sufficiently greater than 1:1 so that, at thecompletion of the process, there are essentially no remaining isocyanategroups.
 48. A process for fusing toner residing on a substrate to thesubstrate, the process comprising: (a) applying, to the surface of afuser member during the toner fusing process, a release agentcomposition comprising a polymer, the polymer comprising: (1) at leastone polyorganosiloxane block; (2) at least one organomer block,comprising at least one member selected from the group consisting ofperhalopolyether blocks and hydrocarbyl blocks; and (3) at least onepolar linkage: (A) comprising a polar functionality having a polarityvalue of at least about 2.0, the polar functionality comprising ahydrogen bond acceptor and a hydrogen bond donor, the hydrogen bonddonor comprising a hydrogen bondable H atom; and (B) covalently bondinga polyorganosiloxane block and an organomer block selected from thegroup consisting of perhalopolyether blocks and hydrocarbyl blocks; and(b) contacting the toner with the fuser member surface bearing therelease agent composition.
 49. The process of claim 48, wherein thepolar functionality comprises an amide incorporating group selected fromthe group consisting of an amide group, a urea group, and a urethanegroup.
 50. A process for fusing toner residing on a substrate to thesubstrate, the process comprising: (a) applying, to the surface of afuser member during the toner fusing process, a release agentcomposition comprising a polymer, the fuser member comprising apolyfluorocarbon surface, the polymer comprising: (1) at least onepolyorganosiloxane block; (2) at least one organomer block selected fromthe group consisting of fluorocarbyl blocks and perfluoropolyetherblocks; and (3) at least one polar linkage: (A) comprising a polarfunctionality having a polarity value of at least about 1.8; and (B)covalently bonding a polyorganosiloxane block and an organomer blockselected from the group consisting of fluorocarbyl blocks andperfluoropolyether blocks; and (b) contacting the toner with the fusermember surface bearing the release agent composition.
 51. A process forfusing toner residing on a substrate to the substrate, the processcomprising: (a) applying separately, to the surface of a fuser member,reactants comprising: (1) a polyorganosiloxane precursor comprising afirst polar linkage forming moiety, the first polar linkage formingmoiety comprising a first polar functionality forming group; and (2) anorganomer precursor comprising at least one member selected from thegroup consisting of perhalopolyether precursors and hydrocarbonprecursors, and further comprising a second polar linkage formingmoiety, the second polar linkage forming moiety comprising a secondpolar functionality forming group; (b) reacting the reactants on thesurface of the fuser member, to form a polymer comprising at least onepolyorganosiloxane block, at least one organomer block comprising atleast one member selected from the group consisting of perhalopolyetherblocks and hydrocarbyl blocks, and at least one polar linkage comprisinga polar functionality having a polarity value of at least about 2.0, thepolar functionality comprising a hydrogen bond acceptor and a hydrogenbond donor, the hydrogen bond donor comprising a hydrogen bondable Hatom, the at least one polar linkage covalently bonding apolyorganosiloxane block and an organomer block selected from the groupconsisting of perhalopolyether blocks and hydrocarbyl blocks; whereinthe first and second polar linkage forming moieties react to form the atleast one polar linkage; with the first and second polar functionalityforming groups reacting to form the polar functionality; and (c)contacting the toner with the fuser member surface bearing the polymer.52. The process of claim 51, wherein: the first polar functionalityforming group comprises one of an amidization reactive carboxyl groupand an amidization reactive primary amine group; and the second polarfunctionality forming group comprises the other of the amidizationreactive carboxyl group and the amidization reactive primary aminegroup; whereby the polyorganosiloxane precursor comprises one of acarboxy functional precursor and a primary amino functional precursor,and the organomer precursor comprises the other of the carboxyfunctional precursor and the primary amino functional precursor; withthe polar functionality comprising an amide group; the processcomprising: (a) applying the primary amino functional precursor to thesurface of the fuser member; (b) applying the carboxy functionalprecursor to the surface of the fuser member, at a position subsequentto the position for application of the primary amino functionalprecursor; whereby the carboxy functional precursor is added to primaryamino functional precursor on the surface of the fuser member; so thatat least essentially all of the amidization reactive primary aminegroups are reacted on the surface of the fuser member, before reachingthe substrate or toner residing on the substrate.
 53. The process ofclaim 52, wherein the ratio of amidization reactive carboxyl groups toamidization reactive primary amine groups is sufficiently greater than1:1 so that at least essentially all of the amidization reactive primaryamine groups are reacted on the surface of the fuser member, beforereaching the substrate or toner residing on the substrate.